IE47301B1 - Catalysts containing iron and molybdenum and the use of these catalysts in the preparation of acrylonitrile or methacrylonitrile - Google Patents

Catalysts containing iron and molybdenum and the use of these catalysts in the preparation of acrylonitrile or methacrylonitrile

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Publication number
IE47301B1
IE47301B1 IE1523/78A IE152378A IE47301B1 IE 47301 B1 IE47301 B1 IE 47301B1 IE 1523/78 A IE1523/78 A IE 1523/78A IE 152378 A IE152378 A IE 152378A IE 47301 B1 IE47301 B1 IE 47301B1
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Ireland
Prior art keywords
catalysts
catalyst
acrylonitrile
methacrylonitrile
mixtures
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Application number
IE1523/78A
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IE781523L (en
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Standard Oil Co
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Publication date
Application filed by Standard Oil Co filed Critical Standard Oil Co
Publication of IE781523L publication Critical patent/IE781523L/en
Publication of IE47301B1 publication Critical patent/IE47301B1/en

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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8872—Alkali or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8875—Germanium, tin or lead
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8876—Arsenic, antimony or bismuth
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention is related to new catalysts containing iron, bismuth, molybdenum and various additional elements which exhibit extremely attractive catalytic properties for the oxidation and ammoxidation of various olefins. The invention is further related to the use of such catalysts in the ammoxidation of propylene and isobutylene to acrylonitrile and respectively, methacrylonitrile.

Description

Technical Field of the Invention The invention is related to new catalysts containing iron, bismuth, molybdenum and various additional elements which exhibit extremely attractive catalytic properties for the oxidation and ammoxidation of various olefins. The invention is further related to the use of such catalysts in the ammoxidation of propylene and isobutylene to acrylonitrile and, respectively, methacrylonitrile.
Background of the Invention Catalysts for the oxidation, ammoxidation and oxydehydrogenation 1θ of olefins are well known. See, for example, U.S. Patents Nos. 3,642,930 and 3,414,631, the disclosures of which are incorporated herein by reference. Further note commonly assigned U.S. Applications Serial No. 490,532, filed 22 July 1974, Serial No. 380,527, filed 19 July 1973 and Serial No. 717,838 filed 26 August 1976, the disclosures of which are also incorporated herein by reference. Although these catalysts of the art are very desirable, the catalysts of the present invention have significant advantages over these other catalysts.
Summary and Detailed Description of the invention.
The present invention is based on the discovery that certain oxidation 20 catalysts based on iron, bismuth and molybdenum and containing additional specified promoter elements exhibit excellent catalytic activity for a variety of olefin oxidation, ammoxidation, dehydrogenation and oxydehydrogenation reactions. In particular, it has been found that specific catalytic compositions as described below are especially suited for use in producing acrylonitrile and methacrylonitrile by the ammoxidation of propylene and isobutylene, respectively. In addition to being excellent ammoxidation catalysts for the production of acrylonitrile or methacrylonitrile, these catalysts also exhibit excellent catalytic activity for the conversion of olefins having four or more contiguous carbon atoms to the corresponding diolefins, and in the oxydehydrogenation of olefins to diolefins. The present invention however is particularly directed to a process for producing acrylonitrile or methacrylonitrile by the reaction of propylene or isobutylene, molecular oxygen and ammonia at a temperature of about 200°C to 600°C in the presence of the novel catalysts of the invention hereinafter defined.
In accordance with the present invention, novel catalysts having improved catalytic properties are represented by the following empirical 15 formula JaVcFedDeMo12°x wherein J is an alkali metal, thallium, silver or mixtures thereof; Q is Co, Ni, Zn, Cd, Be, Hg, Ca, Sr, Ba, Ra or mixtures thereof; Z is a two-or-more element system comprising Cu+W, Cu+Sn, Ce+W, Pr+Mn, Μπ+W, W+Sb, Cr+Sn, W+Sn, Ge+Sn, Sb+Sn, Cr+Cu, Sb+Cu, or mixtures thereof. is Bi or Te; and wherein a is a number from 0.01 to 0.5; b is a number from 0.1 to 20; c is a number from 0.1 to 9; d is a number from 0.1 to 20; e is a number from 0.1 to 20 and x is a value such that the valence requirement of the elements in the catalysts for oxygen are satisfied; each element in said two or more element system being present in an amount of at least 1 atom percent based on the atoms in the system.
In this catalyst composition, the Z component is composed of systems of two or more specified elements. In these systems as described above, each element of the system is present in an amount of at least 1 atom percent, preferably at least 5 atom percent, based on the atoms in the particular system selected. In this catalyst, D is preferably Bi.
Preferably, the catalysts of this invention contain the aboveindicated elements in the following amounts: a is 0.03 to 0.5, b is 4 to 10, c is 0.5 to 7, d is 0.5 to 5, and e is 0.5 to 5.
In a particular preferred embodiment, the foregoing preferred and optimal catalysts contain K, Rd and/or Cs and optionally Ni and/or Co.
Also, it is desirable if Z is selected so that the ratio of the amount of the first element of each system as described above to the amount of second element in the system is 1:0.25 to 1:0.75.
Of the foregoing catalysts, catalyst in which the 5 Z component is selected from the following combinations of elemen ts are of special interest: Cu+W, Cu+Sn, Ce+W, Pr+Mn, W+Sb, Cr+Sn, W+Sn, Ge+Sn, Sb+Sn, Cr+Cu, Sb+Cu or Mn+W; while those catalysts in which Z is one of Cu+W, Cu+Sn, Ce+W and Pr+Mn are particularly noteworthy.
The catalysts of this invention can be prepared in any conventional manner known in the art, such as for example the various techniques shown in the patents and applications referred to in the background of the invention. For example, the catalysts can be made by forming an aqueous composition of decomposable salts and/or oxides of the metals to be incorporated into the catalyst, evaporating the water from the aqueous composition to form a thick paste, drying the thick paste and then calcining the thick paste at elevated temperature in an oxidizing atmosphere.
Techniques for forming catalysts of the type described herein are well known in the art, and those skilled in the art should have no difficulty in making catalysts of the invention.
The catalysts of the present invention may be used unsupported or supported on various conventional carriers such as SiOg, AlgOg, ZrOg, Ti02, SPO^, SbP04, MgO, montmorillonite, or the like. They may be used in fixed-bed or fluid-bed reactors as desired. When using these catalysts, they are simply substituted for the catalysts previously employed, and the reaction is conducted under substantially the same conditions.
For example, when the inventive catalysts are used in the ammoxidation of propylene or isobutylene to form acrylonitrile or methacrylonitrile. respectively, the olefin to be reacted together with oxygen and ammonia in conventional proportions are contacted with the catalyst at an elevated temperature, usually about 200-600°C in a fixed or fluid-bed reactor for a time sufficient to effect the appropriate ammoxidation reaction. Similarly, when the inventive catalysts are employed to catalyze other well known reactions, the reaction conditions employed are those v;hich are conventional.
Specific embodiments Comparative example A 80% Κθ -jHig 5*-°4 5^3^0 5Μο12θχ+2θ^ S^°2 A solution of 127.1 g ammonium heptamolybdate (NH^JgMoyO^.WgO and water was prepared. To this solution was added 6.9 g of a 42.5% solution of H^PO^ and 102.7 g of 40% silica sol to form a slurry.
Separately, an aqueous solution containing 72.7 g ferric nitrate, Fe(N03)3.9H,,0; 29.1 bismuth nitrate, Bi(M03)3 .51^0: 78.6 g cobalt nitrate Co(N03)2 ,6H20; 43.6 nickel nitrate Ni(N03)2 .6H20: and 6.1 g of a 10% potassium nitrate solution was prepared. The solution of metal nitrates v/as slowly added to the slurry. The resulting slurry v/as evaporated to dryness, and the solid obtained v/as heat treated at 290°C for three hours, at 425°C for three hours and at 550°C for 16 hours.
Examples T to 3 In the same manner as discussed in Comparative Example A, catalysts listed in the following Table 1 were prepared. Each of these catalysts as well as Comparative Catalyst A was tested for its catalytic activity in the ammoxidation of propylene to acrylonitrile. In carrying out this test, each of the catalysts was charged into a 5 ccm fixed-bed reactor. A feed of propylene/ammonia/oxygen/nitrogen/steam in amounts of 1.8/2.2/3.6/2.4/6 was fed to the reactor such that the WWH was 0.1 g propylene per gram catalyst per hour and the contact time was three seconds. The reaction temperature was maintained at 420°C. The results obtained as well as the results obtained when Comparative Catalyst A was employed are set forth in the following Table 1.
Table 1 Example Catalyst composition (80% Catalyst supported on 20% Si02) Acrylonitrile per pass conversion Acrylonitril selectivity Comp. AK0.1Nl2.5Co4.5Fe3BlP0.5Mo12°x 73.1 79.4 1MnW0.5^0.1Ni2.5Co4.5Fe2Bl'Mo12°x^ 68.5 86.4 2 SnMnQ.5(Ko.1N i 2.5Co4.5Fe281M°12°x) 76.2 82.8 3PrMn0.5^K0.1Ni2.5Co4.5Fe2BlMo12°x^ 77.9 78.8 The parentheses used in Table 1 as well as the following Table 11 have no significance other than to clarify the difference between the various catalysts.
Examples 4 to 6 Using the various catalysts prepared in the manner described above, additional examples in which propylene was ammoxidized to acrylonitrile were conducted. These additional experiments were conducted in accordance with the same procedure used in Examples 1 to 3, except that the reaction temperature was 430°C, the contact time was 6 seconds and the catalyst support was 50% SiOg. The results obtained are set forth in the following Table 11 Table 11 Example Catalyst composition (80% Catalyst supported on 20% Si0^) Acrylonitrile per pass conversion Acrylonitrile selectivity Comp. AK0.1Ni 2.5Co4.5F43BlP0.5Hol2°x 76.4 79,2 Comp. AK0.1N Y5Co4.5Fe3BlP0.5Mo12°x 76.0 77.8* 4Sn%.5K0.2(Nl2.5Co4.5Fe2Mo120x^ 77.0 77.4 5CeW0. 5l(0.3 12.5C°4. 5Fe2Mol2°x ) 80.0 81.1 6SeSb0.5¾. 3 5Co4.5Fe2Mo12°x) 80.9 82.0* *9 second contact time

Claims (10)

1. Oxidation catalysts characterized by the general formula: at c d e 12 x wherein J is an alkali metal, thallium, silver or mixtures thereof; Q is Co, Ni, Zn, Cd, Be, Mg, Ca, Sr, Ba, Ra or mixtures thereof: Z is a two-or-more element system comprising Cu+W, Cu+Sn, Ce+W, Pr+Mn, Mn+W, W+Sb, Cr+Sn, W+Sn, Ge+Sn, Sb+Sn, Cr+Cu, Sb+Cu, or mixtures thereof; D is Bt or Te; and wherein a is a number from 0.01 to 0.5; b is a number from 0.1 to 20; c is a number from 0.1 to 9; d is a number from 0.1 to 20; e is a number from 0.1 to 20; and x is a value such that the valence requirement of the elements in the catalyst for oxygen are satisfied; each element in said two or more element system being present in an amount of at least 1 atom percent based on the atoms in the system.
2. The catalysts of claim 1 characterized in that 0 is Bi.
3. The catalysts of claim 2 characterized in that Z is either Cu+W, Cu+Sn, Ce+W, Pr+Mn, W+Sb, Cr+Sn, W+Sn, Ge+Sn, Sb+Sn, Cr+Cu, Sb+Cu or Mn+W. 7301
4. The catalysts of claim 2 characterized in that said catalysts contain at least one of K, Rb, and Cs and at least one of Co and Ni.
5. Process for the preparation of acrylonitrile or methacrylonitrile 5 by the reaction of propylene or isobutylene, molecular oxygen and ammonia at a temperature of about 200°C to 600°C in the presence of a catalyst, characterized in that a catalyst is used characterized by the general formula ab c d e 12 x wherein lu J is an alkali metal, thallium, silver or mixtures thereof; Q is Co, 1 Ni, Zn, Cd, Be, Mg, Ca, Sr, Ba, Ra or mixtures thereof; 7 ί S ?, t ' . -.ν’— *·.* siement system coraprisi-.g Se+Sb, · *15 , C ’ Pr+Mn, Cn+Mn, .. '* *r!, J Sc, Cr+Sn, ί-i+Sn, Oe+S; a, Et-in , Ssrf, Cr+Cu, Sti-Cu, η-Ί ;r ...res with ths proviso that said catalyst is free cf Tl ! when Z is Mn+P; D is Bi or Te; ane wherein a is a number from 0.01 to 0.5; ?0 b is a number from 0.1 to 20; c is a number from 0.1 to 9; d is a number from 0.1 to 20; e is a number from 0.1 to 20; and x is a value such that the valence requirement of the elements in 25 the catalyst for oxygen are satisfied; each element in said two or more element system being present in an amount of at least 1 atom percent based on the atoms in the system.
6. Process as claimed in claim 5 wherein D is Bi.
7. Process as claimed in claim 6 wherein J is at least one of K, Rb and Cs md Q is at least one of Co and Ni.
8. An oxidation catalyst substantially as described herein with reference to the Examples.
9. A process for the preparation of acrylonitrile of methacrylonitrile substantially as described herein with reference to the Examples.
10. Acrylonitrile or methacrylonitrile prepared by a process according to any of claims 5 to 7 or 9 using an oxidation catalyst according to any of claims 1 to 4 or 8.
IE1523/78A 1977-07-28 1978-07-27 Catalysts containing iron and molybdenum and the use of these catalysts in the preparation of acrylonitrile or methacrylonitrile IE47301B1 (en)

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EP (1) EP0000564B1 (en)
AT (1) AT363911B (en)
AU (1) AU525163B2 (en)
BR (1) BR7804847A (en)
CA (1) CA1132124A (en)
DD (1) DD137532A5 (en)
DE (1) DE2861849D1 (en)
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EG (1) EG13970A (en)
ES (1) ES471682A1 (en)
FI (1) FI66129C (en)
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IE (1) IE47301B1 (en)
IL (1) IL55073A (en)
IN (1) IN148019B (en)
IT (1) IT1196394B (en)
NO (1) NO150345C (en)
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DE3068189D1 (en) * 1980-07-18 1984-07-19 Mitsubishi Chem Ind Catalytic composition, method for its preparation and its use
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GB2221852A (en) * 1988-08-18 1990-02-21 Ti Corporate Services Vehicle exhaust gas catalysts
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DD137532A5 (en) 1979-09-12
AT363911B (en) 1981-09-10
AU3793078A (en) 1980-01-17
IT1196394B (en) 1988-11-16
IN148019B (en) 1980-09-27
EP0000564B1 (en) 1982-05-19
ATA547778A (en) 1981-02-15
CA1132124A (en) 1982-09-21
FI782285A (en) 1979-01-29
DK333778A (en) 1979-01-29
NO150345B (en) 1984-06-25
ZA783914B (en) 1979-08-29
NO150345C (en) 1984-10-03
PT68312A (en) 1978-08-01
IE781523L (en) 1979-01-28
DE2861849D1 (en) 1982-07-08
FI66129C (en) 1984-09-10
IT7826142A0 (en) 1978-07-26
EG13970A (en) 1983-03-31
EP0000564A1 (en) 1979-02-07
FI66129B (en) 1984-05-31
AU525163B2 (en) 1982-10-21
RO77761A (en) 1981-11-24
IL55073A (en) 1982-01-31
BR7804847A (en) 1979-04-10
NO782582L (en) 1979-01-30
GR66444B (en) 1981-03-23
ES471682A1 (en) 1979-10-01

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