CA1057310A - Selective extraction of triphenylphosphine oxide from oxo-synthesis effluents - Google Patents

Selective extraction of triphenylphosphine oxide from oxo-synthesis effluents

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Publication number
CA1057310A
CA1057310A CA228,921A CA228921A CA1057310A CA 1057310 A CA1057310 A CA 1057310A CA 228921 A CA228921 A CA 228921A CA 1057310 A CA1057310 A CA 1057310A
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Prior art keywords
triphenylphosphine
rhodium
mixture
triphenylphosphine oxide
tails
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CA228,921A
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French (fr)
Inventor
Guglielmo Gregorio
Alberto Andreetta
Maurizio Tampieri
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Montedison SpA
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Montedison SpA
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073—Rhodium compounds
    • C07F15/008—Rhodium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/025—Purification; Separation; Stabilisation; Desodorisation of organo-phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
    • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • 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
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

ABSTRACT OF THE DISCLOSURE:

A process for the selective extraction of triphenyl-phosphine oxide from the distillation tails of an oxo-process, carried out with rhodium carbonyl complexes and triphenylphosphine as a catalyst. The process of the invention is characterized in that a portion of the tails is treated with a solvent mixture composed of water and polar organic compounds selected from the group consisting of alcohols and ketones, at a temperature at least higher than the melting point of the tails, whereby a polar phase containing a substantial portion of triphenylphosphine oxide and another phase rich in triphenylphosphine and containing the rhodium complexes are formed.

Description

This invention relates to a process for the selective extraction of a chemical compound from reaction effluents and, morP
particularly, to a process for selectively extracting triphenyl-phosphine oxide from oxo-synthesis effluents.
Reaction by-products are obtained in the continuous hy-droformylation of olefin to aldehydes in a liquid reaction medium which contains a homogeneous catalytic system including a salt or a hydride of a metal of Group VIII and an organic biphyllic ligand t consisting in particular of triphenylphosphine, in excess with respect to the amount necessary to form the complex. Such by-pro-10ducts accumulate in the distillation tails when the useful products are removed by distillation. These tails are continuously recycled to the reaction ~one.
In order to avoid the accumulation of reaction by-pro-ducts consisting of high-boiling products coming from the condensa-tion of aldehydes and of triphenylphosphine oxide, it is necessary to remove them from a portion of the distillation tails. Some me-thods of removing high-boiling by-products are ~nown, which are based either on osmosis techniques through silicone rubber-based membranes or on adsorption on solid inorganic compounds. Such 20methods are not entirely successful.
It is an object of this invention to provide a novel process for separating triphenylphosphine oxide from by-products ; produced when olefins are converted to aldehydes by hydroformyla-tion. Another object of the invention is to provide a process for selectively extracting triphenylphosphine from the distillation tails remaining after aldehydes produced by hydroformylation of olefins have been xecovered from the reaction medium by distilla-tion. Still another object of the invention is to provide a proJ
cess for recovering the triphenylphosphine oxide of a catalyst sys-30tem used in the hydroformylation of an olefin to form an aldehyde from the by~products produced by the process.
It was now been found that it is possible to selectively ` 1057310 extract by means o~ polar organic solvents the triphenylphosphine oxide from the above described distillation tails containing, besides the high-boiling by-products, free triphenylphosphine and soluble rhodium complexes in the form of hydrides or zero-valent carbonyls bound to the phosphine itself.
The foregoing objects and others are accomplished in accordance with this invention by providing a process for the selective extraction of triphenylphosphine oxide ~rom the distil-lation tails of an oxo-process carried out with rhodium carbonyl complexes and triphenylphosphine as a catalyst. The process of the invention is characterized in that a portion of the tails is treated with a solvent mixture composed of water and polar organic compounds selected from the group consisting of alcohols and ketones, at a temperature at least higher than the melting point of the tails,whereby a polar phase containing a substantial portion of triphenylphosphine oxide and another phase rich in triphenylphosphine and containing the rhodium complexes are formed. The polar solvent phase containing a considerable portion of the triphenylphosphine oxide present in the tails may be subsequently treated in order to recover the organic solvent, and the phase comprising the most part of the catalyst system may be directly recycled to the reaction zone after separation of the residual solvent.
Examples of polar organic compounds having a high - dielectric constant which may be used in accordance with the invention include methyl alcohol, ethyl alcohol, isopropyl alcohol, tertiary butyl alcohol, acetone and methylethyl ketone.
The solvent amount and type suited to the process are selected so as to extract an amount of triphenylphosphine oxide at least sufficient to avoid an accumulation thereof in the reaction zone.

~. ~
LJ

~0573~0 By "solvent type" is meant both a mixture of one of the above-listed compounds with water in various percentages, and a mixture of such compounds with one another and water.
The mixtures which have proved to be particularly advantageous for extracting triphenylphosphine oxide include methyl-alcohol-water mixtures containing 50 to 80% of methylalcohol and acetone-watér mixtures containing 40 to 70% of acetone.
The temperature at which the process of the invention is conducted shall be at least above the melting point of the mixture rich in triphenylphosphine and rhodium complexes, as such mixtures are solid at room temperature. The preferred temperature range is between 50 and 120C.
The amount of triphenylphosphine and rhodium complex that dissolves in the polar phase is very low in any case.
In accordance with one embodiment of the invention, the effluent of a propylene hydroformylation process, carried out with rhodium carbonyl complexes and triphenylphosphine as a catalyst, is subjected to distillation for separating the useful products consisting of C4 aldehydes from the reaction mixture, while the distillation tails xich in triphenylphosphine, rhodium complexes and reaction by-products are recycled to the reaction zone, To avoid the accumulation of triphenylphosphine oxide and aldehyde condensation products, a portion of the high-boiling products (in an amount corresponding at least to the newly-formed one) must be removed. Through conventional distillation processes it is possible to remove the reaction by-products with : the exception of triphenylphosphine oxide without substantially altering the catalyst system.
The portion of residual tails is subjected to an extraction treatment with solvents made up of mixtures of water and polar organic compounds having a high dielectric constant. The tail portion/polar solution ratio is 1/5 to 5 times by volume. The . , . ,Ir ~057310 preferred temperature depends upon the melting point of the treated tails.
Two phases form, i.e. a polar phase containing a sub-stantial portion of triphenylphosphine oxide, which is thus re-moved from the tails, and a phase rich in triphenylphosphine and containing the rhodium complexes. The phase rich in triphenyl-phosphine and containing rhodium complexes may be directly recy-cled to the reaction zone after steam stripping in order to remo-ve the residual solvent, while the polar phase may be treated for recovering the solvent itself and the triphenylphosphine oxide.
A preferred operation method includes also the recovery of small amounts, if any, of the rhodium- triphenylphosphine complex, that may have been extracted with the polar phase. Such recovery may take place by subjecting the polar phase to extrac-tion, at room temperature and atmospheric pressure, with a solvent for the triphenylphosphine-rhodium complex made up of aliphatic and aromatic hydrocarb~ns either pure or admixed with each other.
Any suitable hydrocarbon solvent may be used in the pro-cess such as, for example, n-pentane, n-hexane, n-heptane, isooc-tane, benzene, toluene and the like.
By employing properly selected solvents it is possible to recover the triphenylphosphine and the rhodium complex, while most of the triphenylphosphine oxide remains in the polar phase.
Another possible recovery method involves reducing the solvent power of the polar mixture used to extract the triphenyl-phosphine oxide either by cooling or water addition or both, so as ; to promote the separation of the triphenylphosphine and of the dissolved rhodium complexes, but without reaching a substantial precipitation of the dissolved triphenylphosphine oxide.
The rhodium complex and the triphenylphosphlne thus re-covered are then conveyed to the reaction zone.
The following examples are given to better illustrate ~ OS73~0 ; ~be present invention.

An effluent flowing from a reactor for the hydroformyla-tion of propylene with a soluble catalyst based on rhodium and triphenylphosphine was subjected to distillation in order to sepa-rate the useful products, consisting of n-butyric and isobutyric aldehydes, leaving the high-boiling by-products and the catalyst system in the distillation tails. Most of these tails were conti-nuously recycled to the hydroformylation reactor, while a fraction of them was purged and evaporated under vacuum to remove the most ~ volatile by-products. After such treatment the fraction composi-tion was as follows:
triphenylphosphine and rhodium-triphenylphosphine complexe 65%
products of aldolic condensation of aldehydes15%
triphenylphosphine oxide 20%
This mixture was continuously fed to a container equipped with a 8tirrer and kept at 75C. An aqueous solution containing 70% by wei~ht of methyl alcohol was simultaneously fed continuously to the container at a flow rate corresponding to 0.85 kg per kg of the mixture.
~ The outflowing suspension was sent to a decanter main-tained at 75C, in which two liquid layers separated. The lower layer had the following composition:
triphenylphosphine and rhodium-tri-phenylphosphine complexes 73.2~
aldolic condensation products 11.2%
triphenylphosphine oxide 12.9%
methylalcohol 2.7%
i The upper layer contained:
triphenylphosphine and rhodium-tri-phenylphosphine complexes 2.5%
aldolic condensation products 5.5%
triphenylphosphine oxide 9%

1()573~0 methylalcohol 56%
water 26%
Both liquids were continuously withdrawn separately. The liquid having the higher density, the one containing most of the triphe-nylphosphine and the rhodium - trip~enylphosphine complexes was recycled as such to the hydroformylation reactor. Conversely, the hydroalcoholic phase was cooled down to 25C and filtered:
the triphenylphosphine and the rhodium - txiphnylphosphine com-plexes that separated in the crystalline state were recovered and recycled along with the liquid of the lower phase. The filtered solution contained:

triphenylphosphine and rhodium-tri-phenylphosphine complexes 0.2%
aldolic condensation products 5.6%
triphenylphosphine oxide 9.2%
methylalcohol ~ water 85%
Methanol could be recovered from this solution by separation down-stream of the recovery of the by-products contained therein. The triphenylphosphine oxide extracted and removed through the afore-said operations amounted to 45% of that initially present.

An effluent from a propylene hydroformylation reactor was treated as described in Example 1. The tail fraction, once purged and purified from the most volatile compounds, had the same composition as reported hereinabove:

triphenylphosphine and rhodium-tri-phenylphosphine complexes 65~
aldolic condensation products 15%
triphenylphosphine oxide 20%
This mixture was continuously fed to a container equipped with a stirrer and kept at 75C. Aqueous methylalcohol containing 65%
by weight of methylalcohol was simultaneously fed continuously to the container at a flow rate of 0.87 kg per kg of mixture.

:

The outflowing suspension was conveyed to a decanter kept at 75C, wherein two liquid layers separated. The lower layer had the following composition:

triphenylphosphine and rhodium-tri-phenylphosphine 72.5%
aldolic condensation products 11.4%
triphenylphosphine oxide 14.2%
methylalcohol 2.2%
The upper layer contained:

triphenylphosphine and rhodium-tri-phenylphosphine complexes 1.5~
aldolic condensation products 5.0%
triphenylphosphine oxide 7.5%
methylalcohol 55 water 30~
Eoth liquids were withdrawn continuously in separate streams.
The lower layer was recycled as such to the hydroformylation reactor, ~7hile the flow withdrawn from the hydroalcoholic layer was added, in an amount corresponding to 30% by volume, with a mixture containing 55% by weight of n-hexane and 45~ by weight of benzene. The suspension of the two phases, b~nzene/hexane and water/methylalcohol, was stirred at 25 C and decanted. The aqueous methylalcohol phase contained:

triphenylphosphine and rhodium-tri-phenylphosphine complexes 0.1~
aldolic condensation products 3.8%
triphenylphosphine oxide 6.9%
and could be sent to distillation in order to recover methylalco-hol. The benzene/hexane phase was distilled leaving a residue rich in triphenylphosphine and rhodiurn - triphenylphosphine complexes, that was recycled, along with the main flow, to the hydroformyla-tion reactor. The triphenylphosphine oxide extracted and removed through the abQve-described operation was equal to 36% of the one initia~ly present.

~ XAMPLE 3 A fraction of distilla~ion tails, obtained from a pro-pylene hydroformylation raw effluent and treated as in the fore-; going examples, had the following composition:

triphenylphosphine and rhodium-tri-phenylphosphine complexes 65 aldolic condensation products , 20%
triphenylphosphine oxide 15%
This mixture was fed continuously to a container equipped with a stirrer, at a temperature of 60C, along with 1.5 kg per kg of mixture of an acetone and water solution at 50% by weight. The sus-pension outflowing at 60 C was decanted and the l~yers were drawn off separately. The thicker liquid contained:

triphenylphosphine and rhodium-tri-phenylphosphine complexes 47.5%
aldolic condensation products 13 triphenylphosphine oxide 9 acetone + water 31~
It was possible to distill this liquid to remove acetone and wa-ter, and to use it again as a catalytic solution for the hydro-fon~ylation. The ligher phase contained:

txiphenylphosphine and rhodium-tri-phenylphosphine complexes 0.2%
aldolic condensation products 0.8%
- triphenylphosphine oxide 2.5%
acetone + water 96.5~
and was employable for recovering acetone and removing the by-products present in the solution. The triphenylphosphine oxide removed through this extraction amounted to 20~ of that initially , present.

Aithough the invention is described in detail for the purpose of illustration it is to be understood that such detail ~' is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.

Claims (6)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. Process for the selective extraction of triphenyl-phosphine oxide from the distillation tails of an oxo-process, carried out with rhodium carbonyl complexes and triphenylphosphine as a catalyst, characterized in that a portion of said tails is treated with a solvent mixture composed of water and polar organic compounds selected from the group consisting of alcohols and ketones, at a temperature at least higher than the melting point of said tails, whereby a polar phase containing a substantial portion of triphenylphosphine oxide and another phase rich in triphenylphosphine and containing the rhodium complexes are formed.
2. Process according to claim 1, characterized in that the polar organic compounds are selected from the group consisting of methyl alcohol and acetone.
3. Process according to claim 1, characterized in that the selective extraction is carried out with a solvent made up of a mixture of one of said polar organic compounds with water in different percentages, or of a mixture of said compounds with one another and water.
4. Process according to claim 1, characterized in that the extracted polar phase containing most of the triphenylphosphine oxide is treated at room temperature and atmospheric pressure with a solvent selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, benzene and toluene alone or in admixture with each other in order to recover the rhodium-triphenylphosphine complex dissolved in said phase.
5. Process according to claim 1, characterized in that the extracted polar phase containing most of the triphenylphosphine oxide is subjected to cooling and is added with water in order to recover the rhodium-triphenylphosphine complex dissolved in same.
6. A process for recovering triphenylphosphine oxide from a mixture of triphenylphosphine,rhodium-triphenylphosphine complexes and aldolic condensation products, which comprises mixing said mixture with water and a polar organic solvent which selectively dissolves the triphenylphosphine oxide, maintaining the mixture at a temperature at which it is liquid until triphenylphosphine oxide is dissolved in the solvent, allowing the resulting suspension to separate into two layers, and separating the layers.
CA228,921A 1974-06-11 1975-06-10 Selective extraction of triphenylphosphine oxide from oxo-synthesis effluents Expired CA1057310A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT23850/74A IT1014958B (en) 1974-06-11 1974-06-11 SELECTIVE EXTRACTION OF TRIPHENYLPHOSPHINE OXIDE FROM OXO SINTESI EFFLUENTS

Publications (1)

Publication Number Publication Date
CA1057310A true CA1057310A (en) 1979-06-26

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JP (1) JPS5111745A (en)
BE (1) BE830118A (en)
CA (1) CA1057310A (en)
DE (1) DE2526129A1 (en)
ES (1) ES438380A1 (en)
FR (1) FR2274626A1 (en)
GB (1) GB1502339A (en)
IT (1) IT1014958B (en)
NL (1) NL7506672A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2756321A1 (en) * 1977-12-17 1979-06-28 Basf Ag PROCESS FOR THE PROCESSING OF METHANOLIC-AQUATIC RESIDUES IN SYNTHESES WITH THE AID OF TRIPHENYLPHOSPHONIUM SALTS
GB9626746D0 (en) * 1996-12-23 1997-02-12 Knoll Ag Process
CN109433203B (en) * 2018-09-06 2021-05-14 万华化学集团股份有限公司 Method for regenerating triphenylphosphine through electrolytic reduction

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NL7506672A (en) 1975-12-15
GB1502339A (en) 1978-03-01
IT1014958B (en) 1977-04-30
FR2274626A1 (en) 1976-01-09
FR2274626B1 (en) 1978-02-24
ES438380A1 (en) 1977-01-16
BE830118A (en) 1975-12-11
JPS5111745A (en) 1976-01-30

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