EP0000432A1 - Verfahren zum Durchführen der katalytischen Isomerisierung von monozyklischen methylsubstituierten aromatischen Kohlenwasserstoff-Verbindungen - Google Patents

Verfahren zum Durchführen der katalytischen Isomerisierung von monozyklischen methylsubstituierten aromatischen Kohlenwasserstoff-Verbindungen Download PDF

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Publication number
EP0000432A1
EP0000432A1 EP78300119A EP78300119A EP0000432A1 EP 0000432 A1 EP0000432 A1 EP 0000432A1 EP 78300119 A EP78300119 A EP 78300119A EP 78300119 A EP78300119 A EP 78300119A EP 0000432 A1 EP0000432 A1 EP 0000432A1
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European Patent Office
Prior art keywords
catalyst
process according
zeolite
zsm
feedstock
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Granted
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EP78300119A
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English (en)
French (fr)
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EP0000432B1 (de
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Fritz Arthur Smith
Albert B. Schwartz
Lloyd Lee Breckenridge
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ExxonMobil Oil Corp
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Mobil Oil Corp
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    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
    • C07C5/2732—Catalytic processes
    • C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • 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
    • 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
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • the present invention relates to a process for the vapour-phase catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon feedstock.
  • U.S.Patent 3,856,872 A-recently developed and widely adopted catalyst for use in such processes is taught by U.S.Patent 3,856,872 to be of the ZSM-5 type of zeolite, whereby the process operates at high space velocities. Further, a process utilizing ZSM-5 type zeolites in acid form for vapor-phase conversion of a feedstock containing mixed C 8 aromatics in the absence of added hydrogen is taught by U.S.Patent 3,856,873.
  • the catalyst for use in the process of U.S.Patent 3,293,314 is a solid acidic mixed metal-oxide catalyst, e.g., a silica-alumina mixture, having equilibration (tending to produce equilibrium products) and coke forming activities.
  • a solid acidic mixed metal-oxide catalyst e.g., a silica-alumina mixture
  • equilibration ending to produce equilibrium products
  • coke forming activities Unfortunately, such catalyst materials lose their ability to maintain their equilibration tendency and, therefore, there is a decrease in desirable isomeric products as the catalysts age.
  • a process for effecting catalytic isomerization of monocyclic methyl-substituted aromatic hydrocarbon compounds of from 8 to 10 carbon atoms contained in a feedstock also containing ethylbenzene comprises contacting said feedstock in the vapor phase with a catalyst comprising a crystalline aluminosilicate zeolite having a constraint index within the range of 1 to 12, said zeolite containing hydrogen, hydrogen precursor and/or Group VIII metal cations, at a temperature of 600 o F to 900 0 F, a pressure of 0 psig to 500 psig, a hydrogen/hydrocarbon mole ratio of 0 to 10 and a weight hourly space velocity of 0.1 to 200, said catalyst having been contacted with one or more basic nitrogen compounds or precursors therof, the resulting ratio of nitrogen atoms/aluminum atoms in the zeolite being from 0.01 to 1.0.
  • the preferred zeolites for use in the process are zeolites ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38: they usually constitute from 10 to 90 weight percent of a composite with a binder therefor, such as alumina.
  • the preferred Group VIII metal cations are nickel, iron and/or cobalt.
  • the process is particularly applicable to the isomerisation of a feedstock which contains xylenes.
  • the basic nitrogen compounds or precursors thereof which are particularly favoured are ammonia, alkylamines of from 1 to 40 carbon atoms, alkyldiamines of from 2 to 40 carbon atoms, aromatics amines of from 6 to 40 carbon atoms, pyridine, pyrrolidine and aniline.
  • Their contact with the catalyst may be effected during catalyst preparation, by periodic or continuous addition to the feedstock, by contact with the catalyst in the reactor before commencement of the process, or otherwise.
  • Preferred zeolites for use in the present invention are those with a SiO 2 /Al 2 O 3 mole ratio of at least about 12. Many are very well known. Zeolite ZSM-5, for instanoe,is described in U.S.Specification 3,702,886. Zeolite ZSM-11 is described in U.S.Specification 3, 709 , 979. Zeolite ZSM-12 is described in U.S.Specification 3,970,544. Zeolite ZSM-35 is described in U.S. Specification 4,016,245. Zeolite ZSN-38 is described in U.S.Specification 4,046,859. The significance and definition of "Constraint Index" is also well known from extensive patent literature such as DTOS 2,438,252.
  • the catalysts hereof are selected as those having a crystal framework density, in the dry hydrogen form, of not substantially below about 1.6 grams per cubic centimeter. It has been found that zeolites which satisfy all three of these criteria are most desired for the present process. Therefore, the preferred catalysts of this invention are those having a constraint index as defined above of about 1 to about 12, a silica to alumina ratio of at leat about 12 and a dried crystal density of not less than about 1.6 grams per cubic centimeter.
  • the dry density for known structures may be calculated from the number silicon plus aluminum atoms per 1000 cubic Angstroms, as given, e.g., on page 19 of the article on Zeolite Structure by W. M. Heir.
  • the crystal framework density may be determined by classical pyknometer techniques. For example, it may be determined by immersing the dry hydrogen form of the zeolite in an organic solvent which is not sorbed by the crystal. It is possible that the unusual sustained activity and stability of this class of zeolite is associated with its high crystal anionic framework density of not less than about 1.6 grams per cubic centimeter. This high density of course must be associated with a relatively small amount of free space within the crystal, which might be expected to result in more stable structures. This free space, however, is important as the locus of catalytic activity.
  • Crystal framework densities of some typical zeolites are: The amount of ethylbenzene in the feedstock is usually from about 5 to about 30 weight percent, more usually from about 10 to about 25 weight percent.
  • Specific compounds contemplated for isomerisation include para-xylene, meta-xylene, ortho-xylene, mesitylene (1,3,5-trimethylbenzene) durene (1,2,4,5-tetramethylbenzene), hemimellitene (1,2,3-trimethylbenzene), pseudocumene (1,2,4-trimethylbenzene), prehnitene (l,2,3 t 4-tetramethylbenzene) and isodurene (1,2,3,5-tetramethylbenzene) with the xylene isomers and pseudocumene especially preferred.
  • the nitrogen-containing compounds useful in the present process should be ones which neither react with the charge materials nor possess catalytic activity contrary to the purpose for their use.
  • Said nitrogen-containing compounds may be gaseous, liquid or in the form of a solid dissolved in a suitable solvent, such as, for example, toluene.
  • Non-limiting examples of nitrogen compounds or precursors thereof useful in this invention include, for example, ammonia, alkylamines of from 1 to about 40 carbon atoms, and preferably from 1 to about 10 carbon atoms, e.g. n-propylamine, alkyldiamines of from 2 to about 40 carbon atoms, and preferably from 6 to abouit 20 carbon atoms, aromatic amines of from 6 to about 40 carbon atoms, e.g. aniline, and heterocyclic nitrogen compounds, such as pyridine and pyrrolidine.
  • the catalyst may be contacted with the nitrogen compound in a variety of ways.
  • the nitrogen compound can be contacted with the catalyst during manufacture of the catalyst, prior to introducing the normal feedwtock, or it can be added to the feedstock periodically or continuously. Combinations of these modes of addition are also contemplated.
  • a sodium silicate solution was prepared by mixing 16 parts water and 27.7 parts sodium silicate (28.7 wt.% Si0 2 , 8.9 wt.% Na 2 0, 62.4% H 2 0). The solution was cooled to approximately 15 0 C.
  • An acid solution was prepared by adding 1 part aluminum sulfate (17.2 wt.% A1 2 0 3 ) to 16.4 parts water followed by 2.4 parts sulfuric acid (93 wt.% H 2 S0 4 ) and 1.2 parts NaC1.
  • An organic solution was prepared by adding 1.6 parts n-propyl bromide and 3.1 parts methyl ethyl ketone to 1.9 parts tri-n-propylamine.
  • the zeolite slurry product was diluted with 4-5 parts water per part slurry, allowed to settle and supernatent liquid was drawn off. The settled solids were reslurried to the original volume of the preceding step with water. After settling, the aqueous phase was decanted. This procedure was repeated until the sodium level of the zeolite was less than 1.0 wt.%. The washed zeolite was then filtered, dried and identified as ZSM-5 having a silica/alumina mole ratio of about 70 and a constraint index of about 8.3.
  • the dried zeolite was then mixed with alumina and water. It was then extruded into 1.16" pellets and dried. The extruded material contained 65 parts ZSM-5 per 35 parts alumina, by weight.
  • the dried extrudate was calcined for three hours at 538 0 C in flowing nitrogen. After cooling, the extrudate was contacted with an ammonium nitrate exchange solution (about 0.08 1b NH 4 NO 3 /lb extrudate) for one hour at ambient temperature. This exchange was then repeated until the sodium level was less than 0.05 wt.%. The extrudate was then contacted with a nickel nitrate exchange solution (about 0.1 lb Ni (Ni(NO 3 ) 2 . 6H 2 0/lb extrudate) for two hours at about 80-90 o C. After this exchange, the extrudate was washed, dried and calcined in a flowing 10% air-90% nitrogen mixture at 538°C for six hours.
  • an ammonium nitrate exchange solution about 0.08 1b NH 4 NO 3 /lb extrudate
  • the extrudate was then contacted with a nickel nitrate exchange solution (about 0.1 lb Ni (Ni(NO 3 )
  • 25 cc of the catalyst of Example 1 was further calcined at 1000°F in air for 24 hours and placed in an isothermal, one gallon/day reactor. Pure hydrogen was continuously passed through the reactor without recycle in order to maintain a constant molar ratio between hydrogen and hydrocarbon feedstock at the reactor inlet. A feedstock comprising the components listed in Table 2 was then passed through the reactor under the conditions listed in Table 3, hereinafter presented. Also listed in Table 3 are the results of ten separate material balances over the period of 10.5 days on stream.
  • the zeolite is preferably employed in association with a support or binder material which acts as diluent such as, for example, a porous inorganic oxide support or a clay binder.
  • a support or binder material which acts as diluent
  • binder materials include alumina, zirconia, silica, magnesia, thoria, titania, boria and combinations thereof, generally in the form of dried inorganic oxide gels and gelatinous precipitates.
  • Suitable clay materials include, by way of example, bentonite and kieselguhr.
  • the relative proportion of suitable cyrstalline aluminosilicate zeolite of the total composition of catalyst and binder or support may vary with the zeolite content ranging from between about 10 to about 90 percent by weight and more usually in the range of about 20 to about 80 percent by weight of the composition.
  • Operating conditions employed in the improved process of the present invention are important. Such conditions as temperature, pressure, space velocity, molar ratio of the reactants, hydrogen to hydrocarbon mole ration, and the presence of any feedstock diluents, such as toluene and/or C 9 + recycle material, will have important effects on the process.
  • Fixed or fluid bed contacting may be employed.
  • Example 2 After 10.5 days on stream, the catalyst used in Example 2 was contacted in the same reactor as for Example 2 with a feedstock containing a nitrogen -containing compound, i.e., 1.10-decane diamine as indicated in Table 4, hereinafter presented.
  • the feedstock containing the nitrogen-containing compound was pumped through the reactor for 24 hours at operating conditions of 600 o F, 200 psig,a WHSV of 7 hr- 1 and a hydrogen/hydrocarbon mole ratio of 4.
  • the ratio of nitrogen atoms provided in the feed per aluminum atom in the zeolite component was 3.4.
  • Example 2 Thereafter, the above feedstock without the nitrogen-containing compound was charged to the reactor and at the reaction conditions of Example 2, the catalyst was found to be inactive.
  • the reaction temperature was increased, through increments, up to about 750°F, where a rapid reactivation of the catalyst was observed, as a result of desorption of part of the nitrogen from the catalyst, bringing the ratio of nitrogen atoms/aluminum atom in the zeolite component within the range of 0.01 to 1.0.
  • the temperature was then reduced to 700°F where gradual recovery of catalyst activity was still observable.
  • the reaction conditions and results from 8 material balances over the period of about 8 days on stream appear in Table 5.
  • Example 3 The experiment of Example 3 was continued with a feedstock composed as indicated in Table 6. The conditions for and results from 10 material balances over a period of about 10 days on stream appear in Table 7.
  • Example 9 A catalyst prepared as in Example 1, but not contacted with the nickel nitrate solution, was placed in the reactor used in Examples 2-4. A feedstock composed as described in Table 8 was then passed through the reactor at 25 psig, 600°F, a WHSV of 5 hr- 1 and a hydrogen/hydrocarbon mole ratio of 0 (absence of added hydrogen). The results of this experiment are presented in Table 9.
  • Example 5 The feedstock for Example 5 is then injected with ammonia to the extent that the ratio of nitrogen atoms/aluminum atom in the zeolite is 0.1. The injection of ammonia into the feedstock is stopped after a time and the reaction temperature is increased to 750 o F. Results of this experiment are also presented in Table 9 for comparison with the results from Example 5.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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EP78300119A 1977-07-08 1978-07-05 Verfahren zum Durchführen der katalytischen Isomerisierung von monozyklischen methylsubstituierten aromatischen Kohlenwasserstoff-Verbindungen Expired EP0000432B1 (de)

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US81391177A 1977-07-08 1977-07-08
US813911 1977-07-08

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EP0000432A1 true EP0000432A1 (de) 1979-01-24
EP0000432B1 EP0000432B1 (de) 1983-05-25

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EP78300119A Expired EP0000432B1 (de) 1977-07-08 1978-07-05 Verfahren zum Durchführen der katalytischen Isomerisierung von monozyklischen methylsubstituierten aromatischen Kohlenwasserstoff-Verbindungen

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US (1) US4158676A (de)
EP (1) EP0000432B1 (de)
JP (1) JPS6024771B2 (de)
AR (1) AR223821A1 (de)
CA (1) CA1098918A (de)
DE (1) DE2862267D1 (de)
ES (1) ES471561A1 (de)
IN (1) IN149346B (de)
IT (1) IT1109966B (de)
MX (1) MX4173E (de)
ZA (1) ZA783919B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0021445A2 (de) * 1979-06-29 1981-01-07 Montedison S.p.A. Verfahren zur Herstellung von Zeolithen, durch dieses Verfahren erhaltene Zeolithe und ihre Anwendung bei der Umwandlung von Kohlenwasserstoffen
EP0039205A1 (de) * 1980-04-28 1981-11-04 Mobil Oil Corporation Selektive Herstellung von Dialkylbenzolen

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302323A (en) * 1980-05-12 1981-11-24 Mobil Oil Corporation Catalytic hydroconversion of residual stocks
US4533298A (en) * 1982-12-02 1985-08-06 Westinghouse Electric Corp. Turbine blade with integral shroud
US5100535A (en) * 1987-12-03 1992-03-31 Mobil Oil Corporation Method for controlling hydrocracking operations
US5419830A (en) * 1985-07-26 1995-05-30 Mobil Oil Corporation Method for controlling hydrocracking and isomerization dewaxing
US5043512A (en) * 1988-10-06 1991-08-27 Mobil Oil Corp. Alkylaromatic isomerization process
US5030787A (en) * 1990-01-24 1991-07-09 Mobil Oil Corp. Catalytic disproportionation/transalkylation utilizing a C9+ aromatics feed
US5905181A (en) * 1997-12-29 1999-05-18 Uop Llc Process for the isomerization of paraffins
US6313363B1 (en) 1998-04-10 2001-11-06 Institut Francais Du Petrole Process for isomerizing aromatic compounds containing eight carbon atoms
FR2777207B1 (fr) * 1998-04-10 2000-05-19 Inst Francais Du Petrole Procede d'activation des catalyseurs d'isomerisation des composes aromatiques a huit atomes de carbone
US6333289B1 (en) 1998-04-10 2001-12-25 Institut Francais Du Petrole Process for activating catalysts for isomerizing aromatic compounds containing eight carbon atoms
FR2784686B1 (fr) 1998-09-10 2001-02-23 Inst Francais Du Petrole Procede d'isomerisation des composes aromatiques a huit atomes de carbone en deux etapes successives et utilisant un catalyseur active
US6051744A (en) * 1998-12-17 2000-04-18 Chevron Chemical Company Llc Low pressure hydrodealkylation of ethylbenzene and xylene isomerization
FR2795343B1 (fr) * 1999-06-22 2001-08-03 Inst Francais Du Petrole Procede de pretraitement dans des conditions severes d'un catalyseur a base de zeolithe euo
KR102160602B1 (ko) * 2017-12-27 2020-09-28 한화솔루션 주식회사 탄화수소 함유 용액 내의 방향족 함량의 측정 방법

Citations (3)

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US3856872A (en) * 1973-09-13 1974-12-24 Mobil Oil Corp Xylene isomerization
US3992466A (en) * 1975-08-13 1976-11-16 Mobil Oil Corporation Hydrocarbon conversion
DE2558035A1 (de) * 1975-12-22 1977-06-23 Mobil Oil Corp Kombiniertes verfahren zur katalytischen umwandlung und hydrodealkylierung von kohlenwasserstoffen

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US3293314A (en) * 1965-03-04 1966-12-20 Chevron Res Equilibration of lower alkyl substituted aromatic hydrocarbons
US3644200A (en) * 1968-12-23 1972-02-22 Union Oil Co Ammoniated zeolite catalysts
US3856873A (en) * 1973-09-13 1974-12-24 Mobil Oil Corp Xylene isomerization

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3856872A (en) * 1973-09-13 1974-12-24 Mobil Oil Corp Xylene isomerization
US3992466A (en) * 1975-08-13 1976-11-16 Mobil Oil Corporation Hydrocarbon conversion
DE2558035A1 (de) * 1975-12-22 1977-06-23 Mobil Oil Corp Kombiniertes verfahren zur katalytischen umwandlung und hydrodealkylierung von kohlenwasserstoffen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0021445A2 (de) * 1979-06-29 1981-01-07 Montedison S.p.A. Verfahren zur Herstellung von Zeolithen, durch dieses Verfahren erhaltene Zeolithe und ihre Anwendung bei der Umwandlung von Kohlenwasserstoffen
EP0021445B1 (de) * 1979-06-29 1984-01-18 Montedison S.p.A. Verfahren zur Herstellung von Zeolithen, durch dieses Verfahren erhaltene Zeolithe und ihre Anwendung bei der Umwandlung von Kohlenwasserstoffen
EP0039205A1 (de) * 1980-04-28 1981-11-04 Mobil Oil Corporation Selektive Herstellung von Dialkylbenzolen

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IT1109966B (it) 1985-12-23
JPS5419921A (en) 1979-02-15
AR223821A1 (es) 1981-09-30
ES471561A1 (es) 1979-01-16
CA1098918A (en) 1981-04-07
EP0000432B1 (de) 1983-05-25
DE2862267D1 (en) 1983-07-07
IN149346B (de) 1981-10-31
MX4173E (es) 1982-01-15
IT7825466A0 (it) 1978-07-07
ZA783919B (en) 1980-02-27
JPS6024771B2 (ja) 1985-06-14
US4158676A (en) 1979-06-19

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