CA1116587A - Oxyhalogenation process - Google Patents
Oxyhalogenation processInfo
- Publication number
- CA1116587A CA1116587A CA000310423A CA310423A CA1116587A CA 1116587 A CA1116587 A CA 1116587A CA 000310423 A CA000310423 A CA 000310423A CA 310423 A CA310423 A CA 310423A CA 1116587 A CA1116587 A CA 1116587A
- Authority
- CA
- Canada
- Prior art keywords
- composition
- palladium
- range
- atomic ratio
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J23/78—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 alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/15—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination
- C07C17/152—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons
- C07C17/156—Preparation of halogenated hydrocarbons by replacement by halogens with oxygen as auxiliary reagent, e.g. oxychlorination of hydrocarbons of unsaturated hydrocarbons
Abstract
ABSTRACT OF THE DISCLOSURE
Oxychlorination of ethylene to give vinyl chloride in a single step in the presence of a catalyst containing compounds of palladium, copper, iron, alkali metal and rare earth metals.
Oxychlorination of ethylene to give vinyl chloride in a single step in the presence of a catalyst containing compounds of palladium, copper, iron, alkali metal and rare earth metals.
Description
5~37 1. MD 29779 This invention relates to the manufacture of mono-halogenated olefinic compounds by the oxyhalogenation o~ the corresponding olefines. The invention is also concerned with a catalyst composition useful in such a process.
Processes for the manufacture of monohalogenated olefines by the oxyhalogenation of the corresponding olefine have been beset with difficulties. This is particularly true with the oxychlorination of mono-olefines especially of ethy.lene. There is everyincentive to provide an efficient process for the oxychlorination of ethylene in a single stage to give vinyl chloride as the major product. Indeed very many attempts have been made with much expenditure of time and money to provide such a process. Such attempts in the main have been directed at providing an effective catalyst for the oxychlQrination process. Many combinations o catalysts and co-catalyst have been proposed. For example catalysts have been proposed comprising a compound of palladium and copper. However processes based on the use of known catalysts do have severe disadvanta~es. Thus in the oxychlorination of ethylene the disadvantages include poor convPrsions 5~7
Processes for the manufacture of monohalogenated olefines by the oxyhalogenation of the corresponding olefine have been beset with difficulties. This is particularly true with the oxychlorination of mono-olefines especially of ethy.lene. There is everyincentive to provide an efficient process for the oxychlorination of ethylene in a single stage to give vinyl chloride as the major product. Indeed very many attempts have been made with much expenditure of time and money to provide such a process. Such attempts in the main have been directed at providing an effective catalyst for the oxychlQrination process. Many combinations o catalysts and co-catalyst have been proposed. For example catalysts have been proposed comprising a compound of palladium and copper. However processes based on the use of known catalysts do have severe disadvanta~es. Thus in the oxychlorination of ethylene the disadvantages include poor convPrsions 5~7
2. MD 29779 based on starting material, especially based on a chlorinating agent, poor selectivities to the desired vinyl chloride product, production o~ considerable amounts of undesired by-products or considerable S burning of ethylene to give carbon oxides.
It is an object of the present invention to provide a novel, much improved oxyhalogenation process wherein said disadvantages are very much reduced and as such the process proYides a most valuable contribution to the art.
According to one aspect of the invention we provide a process for the oxyhalogenation of a feedstock comprising an olefine to gi~e a monohalogenated olefine which comprises bringing into reaction at elevated temperature in the gas phase an olefine with a source of halogen and molecular oxygen in the presence of a supported catalyst composition comprising a compound of palladium, a compound of copper, a compound of iron and a compound of an alkali metal.
It is preferred to include in the catalyst composition a compound of a rare earth metal.
Compounds of different rare earth metals may be employed. One suitable compound of a rare earth metal contains a significant amount of a compound of cerium.
As illustrative of the compounds of the alkali metals compounds of sodium and lithium may be mentioned. A
compound of sodium is preferred.
The compounds of the metals incorporated in the catalyst composition are suitably but not necessarily the halides corresponding to the halogen of the mono-halogenated compound which is produced. In an oxy-chlorination process, for example of ethylene the compounds of the metals are suitably the chlorides.
It is an object of the present invention to provide a novel, much improved oxyhalogenation process wherein said disadvantages are very much reduced and as such the process proYides a most valuable contribution to the art.
According to one aspect of the invention we provide a process for the oxyhalogenation of a feedstock comprising an olefine to gi~e a monohalogenated olefine which comprises bringing into reaction at elevated temperature in the gas phase an olefine with a source of halogen and molecular oxygen in the presence of a supported catalyst composition comprising a compound of palladium, a compound of copper, a compound of iron and a compound of an alkali metal.
It is preferred to include in the catalyst composition a compound of a rare earth metal.
Compounds of different rare earth metals may be employed. One suitable compound of a rare earth metal contains a significant amount of a compound of cerium.
As illustrative of the compounds of the alkali metals compounds of sodium and lithium may be mentioned. A
compound of sodium is preferred.
The compounds of the metals incorporated in the catalyst composition are suitably but not necessarily the halides corresponding to the halogen of the mono-halogenated compound which is produced. In an oxy-chlorination process, for example of ethylene the compounds of the metals are suitably the chlorides.
3. MD 29779 In use in the oxychlorination process the composition may exist as a mi~ture of chlorides, oxychlorides, oxides and hydroxides. Compounds of metals such as nitrates, oxides, carbonates, oxalates and acetates may also be employed which are converted to the chlorides or said mixtures containing chlorides under the oxychlorination conditions.
Each component of the present catalyst composition has an intricate relationship with one or more of the components of the catalyst composition. ~hile theories can be propounded by way of explaining the relationship the practical result is that unless all of the components are present the improved results of the present process will not be achieved. When the rare earth compound is incorporated in the catalyst composition said compound also shares a relationship with one or more of the other components of the composition and in turn contributes a beneficial result in the efficiency of the process.
~0 We find according to a further and most valuable feature of the invention that there is an intricate relationship between the atomic ratios of the various metals in the present catalyst composition. When using these atomic ratios and particularly when ~5 using the preferred atomic ratios the advantages of the present process become more apparent. These advantages include high conversions of the chlorinating agent, high selectivities, comparitively low formation rates of undesired products e.g~ dichloro-ethylene and 1,1,2-trichloroethane and comparitively low burning of ethylene. Such advantages have not been obtained in prior processes.
Each component of the present catalyst composition has an intricate relationship with one or more of the components of the catalyst composition. ~hile theories can be propounded by way of explaining the relationship the practical result is that unless all of the components are present the improved results of the present process will not be achieved. When the rare earth compound is incorporated in the catalyst composition said compound also shares a relationship with one or more of the other components of the composition and in turn contributes a beneficial result in the efficiency of the process.
~0 We find according to a further and most valuable feature of the invention that there is an intricate relationship between the atomic ratios of the various metals in the present catalyst composition. When using these atomic ratios and particularly when ~5 using the preferred atomic ratios the advantages of the present process become more apparent. These advantages include high conversions of the chlorinating agent, high selectivities, comparitively low formation rates of undesired products e.g~ dichloro-ethylene and 1,1,2-trichloroethane and comparitively low burning of ethylene. Such advantages have not been obtained in prior processes.
4. MD 29779 It is preferred to employ an atomic ratio of palladium to copper in the range 1 atom of palladium to 0.25 to 10 atoms of copper. Typical catalysts contain 1 atom of palladium per 1 to 3 atoms of copper and in particular 1.7 to 2.8 atoms of copper.
The atomic ratio of iron to palladium is suitably in the range 1:1 to 20:1. Preferably this atomic ratio is in the range 4 to 10 atoms of iron per atom of palladium.
The atomic ratio of rare earth metal to palladium is suitably in the range 1.1 to 15.1. Preferably this atomic ratio is in the range 3:1 to 8:1.
The atomic ratio of alkali metal to palladium is suitably in the range 10:1 to 30:1. Preferably this atomic ratio is in the range 15:1 to 25:1.
The proportion by weight of palladium based on the supported catalyst is preferably in the range 0.05%
to 0.5%.
The catalyst may be supported on known carriers such as for example silica and alumina. The surface area of the support can be varied widely but is usually in the range 0.1 to 2C m2/g.
The supported catalyst may be employed in fixed, moving or fluidised beds and of appropriate particle size.
The feed stock employed in the present invention is essentially olefinic~ Olefine reactants which can be employed include for example, ethylene, propylene, straight and branched-chain olefines containing four or more carbon atoms and cyclic o'efine such as cyclohexene.
S~7
The atomic ratio of iron to palladium is suitably in the range 1:1 to 20:1. Preferably this atomic ratio is in the range 4 to 10 atoms of iron per atom of palladium.
The atomic ratio of rare earth metal to palladium is suitably in the range 1.1 to 15.1. Preferably this atomic ratio is in the range 3:1 to 8:1.
The atomic ratio of alkali metal to palladium is suitably in the range 10:1 to 30:1. Preferably this atomic ratio is in the range 15:1 to 25:1.
The proportion by weight of palladium based on the supported catalyst is preferably in the range 0.05%
to 0.5%.
The catalyst may be supported on known carriers such as for example silica and alumina. The surface area of the support can be varied widely but is usually in the range 0.1 to 2C m2/g.
The supported catalyst may be employed in fixed, moving or fluidised beds and of appropriate particle size.
The feed stock employed in the present invention is essentially olefinic~ Olefine reactants which can be employed include for example, ethylene, propylene, straight and branched-chain olefines containing four or more carbon atoms and cyclic o'efine such as cyclohexene.
S~7
5. MD 29779 A particularly suitable olefine for use in the present invention is ethylene. The olefine may also contain a saturated hydrocarbon component, for example, commercially available feedstocks consisting S essentially of ethylene but also containing a small proportion of ethane.
The reaction temperatures employed are dependent to a considerable extent on the reactant employed.
With ethylene suitable reaction temperatures are in the range ~50~C to 400C, preferably 300C to 370C.
The source of chlorinating agent in the present process may be chlorine, hydrogen chloride or substances such as ammonium chloride which on heating decompose to give hydrogen chloride. More suitably the source of the chlorinating agent is hydrogen chloride.
The source of oxygen may be oxygen itself, air or oxygen enriched air. When using oxygen itself the oryanic product, by-products and water are removed and the residual exit gases after suitable monitoring and analysing can be returned to the system.
The molar ratios of ethylene, oxygen and hydrogen chloride are preferably such as to provide 0.5 to 1 mole of oxygen and 009 to 1.5 moles hydrogen chloride for each mole of ethylene. Most suitably the relative proportion of ethylene: hydrogen chloride is approximately 1:1.
In the present process the desired products can be recovered by conventional means. Any dichloroethanes in the crude organic product can be recycled thereby giving more of a desired vinyl chloride product.
The present invention also includes a supported oxychlorination catalyst composition as hereinbefore described.
The following Examples illustrate the invention.
The reaction temperatures employed are dependent to a considerable extent on the reactant employed.
With ethylene suitable reaction temperatures are in the range ~50~C to 400C, preferably 300C to 370C.
The source of chlorinating agent in the present process may be chlorine, hydrogen chloride or substances such as ammonium chloride which on heating decompose to give hydrogen chloride. More suitably the source of the chlorinating agent is hydrogen chloride.
The source of oxygen may be oxygen itself, air or oxygen enriched air. When using oxygen itself the oryanic product, by-products and water are removed and the residual exit gases after suitable monitoring and analysing can be returned to the system.
The molar ratios of ethylene, oxygen and hydrogen chloride are preferably such as to provide 0.5 to 1 mole of oxygen and 009 to 1.5 moles hydrogen chloride for each mole of ethylene. Most suitably the relative proportion of ethylene: hydrogen chloride is approximately 1:1.
In the present process the desired products can be recovered by conventional means. Any dichloroethanes in the crude organic product can be recycled thereby giving more of a desired vinyl chloride product.
The present invention also includes a supported oxychlorination catalyst composition as hereinbefore described.
The following Examples illustrate the invention.
6. MD 29779 The support for the catalyst was an alpha-alumina of surface area 0.6 m2/g and of particle size in the range 50 to 100 ~m. To a weak solution of hydrochloric acid were added 0.5g Pd C12, 0.48g Cu C122H20, 3.65g Fe C13, 6.3g Ce C13.7H20 and 3.95g NaCl. 120g of the support were added to the solution containing the metal chlorides. The mixture was stirred continuously at 100C to 150C for a period of 1/2 hour to 1 hour by which time the catalyst (Catalyst A) was dry.
Other catalysts were prepared in a similar manner and are disclosed in Table I.
TABLE I
Atomic Ratios of Metals Catalyst Pd Cu Fe Ce Na A 1 ] 8 6 24 C 1 ~l 3 5 16 E 1 7. 5 8 21 The apparatus comprised a vertical, heat-resistant glass tube 30cm long and 2.5cm diameter surmounted by an electric furnace. The tube contained 95g of the catalyst(s). Ethylene, hydrogen chloride and air were passed separately into the tube and maintained the catalyst in fluidised bed conditions and product was recovered and analysed by conventional means.
Other catalysts were prepared in a similar manner and are disclosed in Table I.
TABLE I
Atomic Ratios of Metals Catalyst Pd Cu Fe Ce Na A 1 ] 8 6 24 C 1 ~l 3 5 16 E 1 7. 5 8 21 The apparatus comprised a vertical, heat-resistant glass tube 30cm long and 2.5cm diameter surmounted by an electric furnace. The tube contained 95g of the catalyst(s). Ethylene, hydrogen chloride and air were passed separately into the tube and maintained the catalyst in fluidised bed conditions and product was recovered and analysed by conventional means.
7~ MD 29779 The ratio (air calculated as oxygen) of C2H4:HCl:02 was 1:1:0.87.
The temperature conditions and results were as shown in Table II.
TABLE II
TempC Catalyst % conversion Selectivity % v/v Burnin~
of HCl to specific products VC l,l-di EDC C02 364 A 91.5 47.8 9.6 32.2 8.7 362 B 91.6 57.5 4.6 29.0 7.1 365 C 90.6 40.9 8.5 36.5 1~
365 D 86~4 44.0 7.5 36.7 12.2 361 E 83.2 56.9 9.0 ~2.0 12.1 362 F 84.2 51.7 9.0 27.1 12.2 CONVERSION
By way of comparison three catalyst G, H and I were prepared in the broad manner described in Example 1 but which did not contain all the necessary components of the catalysts according to the invention. They were as disclosed in Table III.
TABLE III
Atomic Ratios of Metals 25 Catalyst Pd Cu Fe Ce Na 5~-~
The temperature conditions and results were as shown in Table II.
TABLE II
TempC Catalyst % conversion Selectivity % v/v Burnin~
of HCl to specific products VC l,l-di EDC C02 364 A 91.5 47.8 9.6 32.2 8.7 362 B 91.6 57.5 4.6 29.0 7.1 365 C 90.6 40.9 8.5 36.5 1~
365 D 86~4 44.0 7.5 36.7 12.2 361 E 83.2 56.9 9.0 ~2.0 12.1 362 F 84.2 51.7 9.0 27.1 12.2 CONVERSION
By way of comparison three catalyst G, H and I were prepared in the broad manner described in Example 1 but which did not contain all the necessary components of the catalysts according to the invention. They were as disclosed in Table III.
TABLE III
Atomic Ratios of Metals 25 Catalyst Pd Cu Fe Ce Na 5~-~
8. MD 29779 Runs were carried as described in Example 2 and the results are shown in Table IV.
TABLE IV
Temp Catalyst % conversion Selectivity ~ v/v Burning S of HCl to specific products VC l,l-di EDC C02 362C G 34.6 54.11.76 14.7 29.5 367C H 78.9 34.212.5 38.2 14.6 361C I 44.7 60.53.6 11.9 23.7 In the above Examples, VC means Vinyl Chloride l,l-di means l,l-dichloroethane EDC means 1,2-dichloroethane
TABLE IV
Temp Catalyst % conversion Selectivity ~ v/v Burning S of HCl to specific products VC l,l-di EDC C02 362C G 34.6 54.11.76 14.7 29.5 367C H 78.9 34.212.5 38.2 14.6 361C I 44.7 60.53.6 11.9 23.7 In the above Examples, VC means Vinyl Chloride l,l-di means l,l-dichloroethane EDC means 1,2-dichloroethane
Claims (19)
1. An oxychlorination catalyst composition compri-sing a compound of palladium, a compound of copper, a compound of iron and a compound of an alkali metal, the said compounds being carried upon a support material and being chlorides of the said metals or compounds capable of being at least partially converted into the chlorides under oxychlorination conditions.
2. A composition as claimed in Claim 1 wherein a compound of a rare earth metal is also incorporated.
3. A composition as claimed in Claim 1 wherein the alkali metal compound is a sodium compound,
4. A composition as claimed in Claim 1, 2 or 3 wherein the atomic ratio of copper to palladium is in the range from 0.25:1 to 10:1.
5. A composition as claimed in Claim 1, 2 or 3 wherein the atomic ratio of copper to palladium is from 1:1 to 3:1.
6. A composition as claimed in Claim 1, 2 or 3 wherein the atomic ratio of copper to palladium is in the range from 1.7:1 to 2.8:1
7. A composition as claimed in Claim 1, 2 or 3 wherein the atomic ratio of iron to palladium is in the range from 1:1 to 20:1.
8. A composition as claimed in Claim 1, 2 or 3 wherein the atomic ratio of iron to palladium is in the range from 4:1 o 10:1.
9. A composition as claimed in Claim 2 wherein the atomic ratio of rare earth metal to palladium is in the range from 1:1 to 15:1.
10. A composition as claimed in Claim 9 wherein the atomic ratio of rare earth metal to palladium is in the range from 3:1 to 8:1.
11. A composition as claimed in Claim 1, 2 or 3 wherein the atomic ratio of alkali metal to palladium is in the range from 10:1 to 30:1.
12. A composition as claimed in Claim 1, 2 or 3 wherein the atomic ratio of alkali metal to palladium is in the range from 15:1 to 25:1.
13. A composition as claimed in Claim 1, 2 or 3 wherein the proportion of palladium in the supported catalyst composition is in the range from 0.05% to 5% by weight.
14. A composition as claimed in Claim 1, 2 or 3 wherein the compounds of the metals are the chlorides.
15. A process for the production of vinyl chloride by oxychlorination of ethylene which comprises bringing ethylene into reaction with molecular oxygen and a source of chlorine in the gas phase at elevated temperature in the presence of a catalyst composition as claimed in Claim 1.
16. A process as claimed in Claim 15 wherein the source of chlorine is hydrogen chloride.
17. A process according to Claim 15 which is carried out at a reaction temperature in the range 250°C
to 400°C.
to 400°C.
18. A process according to Claim 17 which is carried out at a reaction temperature in the range 330°C
to 370°C.
to 370°C.
19. A process as claimed in Claim 16 in which the molar ratios of ethylene, oxygen and hydrogen chloride are such as to provide 0.5 to 1 mole of oxygen and 0.9 to 1.5 moles hydrogen chloride for each mole of ethylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB37132/77 | 1977-09-06 | ||
| GB3713277 | 1977-09-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1116587A true CA1116587A (en) | 1982-01-19 |
Family
ID=10393996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000310423A Expired CA1116587A (en) | 1977-09-06 | 1978-08-31 | Oxyhalogenation process |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5455505A (en) |
| AU (1) | AU521294B2 (en) |
| CA (1) | CA1116587A (en) |
| DE (1) | DE2837514A1 (en) |
| FR (1) | FR2401891A1 (en) |
| NL (1) | NL7808938A (en) |
| ZA (1) | ZA784827B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI561299B (en) * | 2015-04-02 | 2016-12-11 | Formosa Plastics Corp | A catalyst for preparing vinyl chloride and a method for preparing vinyl chloride |
| EP3750847A4 (en) * | 2018-03-13 | 2021-03-31 | Lg Chem, Ltd. | Partial oxidation process of hydrocarbons |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1244481A (en) * | 1984-05-24 | 1988-11-08 | Angelo J. Magistro | Catalytic dehydrohalogenation process |
| TWI255736B (en) * | 2002-02-05 | 2006-06-01 | Basf Ag | A catalyst composition for the oxychlorination of ethylene and its use |
| JP5585987B2 (en) | 2011-02-25 | 2014-09-10 | 三菱重工コンプレッサ株式会社 | Compressor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5112204A (en) * | 1974-07-17 | 1976-01-30 | Shigetaro Yamaoka | JUSHITOTSUPANNORENZOKUSEIZOHO |
-
1978
- 1978-08-24 ZA ZA00784827A patent/ZA784827B/en unknown
- 1978-08-28 DE DE19782837514 patent/DE2837514A1/en not_active Withdrawn
- 1978-08-30 AU AU39368/78A patent/AU521294B2/en not_active Expired
- 1978-08-31 CA CA000310423A patent/CA1116587A/en not_active Expired
- 1978-08-31 NL NL7808938A patent/NL7808938A/en not_active Application Discontinuation
- 1978-09-05 FR FR7825488A patent/FR2401891A1/en active Pending
- 1978-09-06 JP JP10868678A patent/JPS5455505A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI561299B (en) * | 2015-04-02 | 2016-12-11 | Formosa Plastics Corp | A catalyst for preparing vinyl chloride and a method for preparing vinyl chloride |
| EP3750847A4 (en) * | 2018-03-13 | 2021-03-31 | Lg Chem, Ltd. | Partial oxidation process of hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2837514A1 (en) | 1979-03-15 |
| AU3936878A (en) | 1980-03-06 |
| NL7808938A (en) | 1979-03-08 |
| AU521294B2 (en) | 1982-03-25 |
| ZA784827B (en) | 1979-08-29 |
| JPS5455505A (en) | 1979-05-02 |
| FR2401891A1 (en) | 1979-03-30 |
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