GB1602669A - Production of phenols - Google Patents
Production of phenols Download PDFInfo
- Publication number
- GB1602669A GB1602669A GB24190/78A GB2419078A GB1602669A GB 1602669 A GB1602669 A GB 1602669A GB 24190/78 A GB24190/78 A GB 24190/78A GB 2419078 A GB2419078 A GB 2419078A GB 1602669 A GB1602669 A GB 1602669A
- Authority
- GB
- United Kingdom
- Prior art keywords
- process according
- catalyst
- alkali metal
- aromatic carboxylic
- benzoic acid
- 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
- 150000002989 phenols Chemical class 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 239000005711 Benzoic acid Substances 0.000 claims description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 11
- 235000010233 benzoic acid Nutrition 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001559 benzoic acids Chemical class 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 aromatic carboxylic acids Chemical class 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- MHCVCKDNQYMGEX-UHFFFAOYSA-N 1,1'-biphenyl;phenoxybenzene Chemical compound C1=CC=CC=C1C1=CC=CC=C1.C=1C=CC=CC=1OC1=CC=CC=C1 MHCVCKDNQYMGEX-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910008334 ZrO(NO3)2 Inorganic materials 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- 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
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms
- C07C37/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions decreasing the number of carbon atoms by replacing a carboxyl or aldehyde group by a hydroxy group
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
(54) IMPROVEMENTS IN OR RELATING TO THE
PRODUCTION OF PHENOLS
(71) We, THE LUMMUS COMPANY, of 1515 Broad Street, Bloomfield, New
Jersey 07003, United States of America, a Company organised and existing under the laws of the State of Delaware, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates to the production of phenols, and more particularly to the oxidation of aromatic carboxylic acids to phenols.
In U.S. Patent Specification Nos. 2,727,026 and 2,852,567, there are described processes for producing phenols from aromatic carboxylic acids which employ a catalyst including copper oxide. The present invention is directed to an improved process for oxidising an aromatic carboxylic acid to a phenol.
According to the present invention there is provided a process for catalytically oxidizing an aromatic carboxylic acid, being benzoic acid or an alkyl-substituted benzoic acid, to the corresponding phenol, the process comprising the steps of: contacting said aromatic carboxylic acid with oxygen and steam in the presence of a catalyst at a temperature of from 200"C to 4000 C and at a pressure of from 2 to 20 atmospheres, with an oxygen to carboxyl group mole ratio of from 0.2:1 to 10:1, and a steam to carboxyl group mole ratio of from 5:1 to 500:1, said catalyst comprising copper, zirconium and an alkali metal all in an oxidised state wherein the copper:zirconium:alkali metal atomic ratio is from 1:0.2 to 0.5:0.5 to 2.5.
The alkali metal is preferably sodium, potassium or lithium.
The catalyst is referred to as being copper, zirconium and an alkali metal, all in an oxidised state, and such catalyst contains such metals and oxygen. The metals may be present as a mixture of the oxides of copper, zirconium and an alkali metal or as a complex thereof, and such terminology encompasses such mixtures and complexes.
More particularly, the catalyst of the oxidised copper, zirconium and alkali metal can be employed in the absence or presence of a suitable support material.
Thus, for example, the catalyst may be in the form of pellets or extrudates, or supported on a support material preferably having a surface area of no greater than 50 m2/g; preferably cr-alumina.
The catalyst includes the three components in an amount effective to catalyse the oxidation of an aromatic carboxylic acid.to the corresponding phenol.
The catalyst may be prepared by a variety of procedures known in the art.
Thus, for example, the catalyst can be supported on a suitable support by an impregnation or a spray drying technique. Alternatively, the three catalyst components can be produced in the form of pellets or extrudates. In preparing supported catalyst by impregnation, for example, water soluble salts of zirconium and copper, such as the nitrates, are dissolved in water and the solution employed to impregnate a suitable support, such as alpha-alumina.
The impregnated support is dried and calcined to oxidise the copper and zirconium. The resulting catalyst is then treated with an aqueous solution of an alkali metal salt, e.g. the hydroxide, followed by drying and calcination to effect oxidation.
In a process in accordance with the present invention, for the oxidation of an aromatic carboxylic acid to the corresponding phenol. The aromatic nucleus may include more than one carboxyl substituent group or may include other substituent groups, such as alkyl or halo. The preferred starting materials are the mono carboxylic acids of benzene and alkyl benzenes. If the starting material is an alkyl substituted benzoic acid the product will be a cresol, whereas if the starting material is merely benzoic acid the product will be phenol.
The oxidation is effected with molecular oxygen which can be provided as such or in admixture with other gases; e.g. as air. The oxygen is employed in at least stoichiometric proportions; however, lesser or greater amounts could be employed.
In general, oxygen is employed in an amount to provide an oxygen to carboxyl groups mole ratio of from 0.2:1 to 10:1, and preferably from 0.5:1 to 5:1.
The reaction is generally effected in the vapour phase in the presence of steam as a diluent. The steam also functions to minimise the production of esters that result from the reaction of the carboxylic acid and the product phenol. The steam is generally provided in an amount corresponding to a steam/carboxyl group mole ratio of 5:1 to 500:1 and preferably 10:1 to 100:1.
The oxidation is effected at temperatures of from 200 to 4000C, and preferably from 250 to 3500C.
The catalytic oxidation can be readily effected by the use of any one of a wide variety of vapour-solid contact systems, e.g., employing the catalyst as a fixed or fluidised bed or in a transfer line type of contact system. The above means for effecting the reaction and others should be apparent to those skilled in the art from the present teachings.
The invention will be further described with respect to the following examples:
EXAMPLE I
Production of Catalyst
12.0 g (0.05 mol) Cu(NO3)2 . 3H2O and 18.0 g (0.025 mol) ZrO(NO3)2 . 5H2O were dissolved in 30 g of water and heated to 7e80"C. The solution was used to impregnate 100 g of a low surface area alpha-alumina (Carborundum SAHT 99, 48 mesh). The wet catalyst was dried and calcined at 7500C for two hours, during which time the nitrates decomposed to their corresponding oxides. This catalyst (100 g) was treated with a solution of 4.3 g (0.077 mol) KOH in 30 g of water. The resulting catalyst was dried and calcined at 5000C for approximately 16 hours. The finished catalyst had the following composition (wt.%): 4.0% CuO, 3.0% ZrO2, 3.6%
K2O remainder alumina.
EXAMPLE II The activity and selectivity of the catalyst in Example I for producing phenol from benzoic acid were measured in a fixed bed reactor. The reactor was a jacketed l'xl" dia. 316 stainless steel tube. Boiling Dowtherm was used in the jacket for temperature control. ["Dowtherm" is a Trade Mark'?]. The feed was prepared by metering water through a heater at reactor pressure, passing the steam so produced through a benzoic acid saturator maintained at a temperature required to give the desired benzoic acid/water ratio, and then mixing this stream with the desired amount of air. The reactor contained 60 g of catalyst. Operating conditions and results are given in Table I.
TABLE I
Feed Composition Selectivities, mole %
Run Time, (mole ratio) Space Velocity, Space Yield, Diphenyl
Temp. C Press. psig hrs. COOH H2O (air)O2 GHSV (STP), hr-1 Conversion % g/g cat/hr. Benzene Phenol oxide 280-310 90-100 3.0 1 38 0.6 2630 35.1 0.0816 2.3 76.1 5.4 280-310 120 3.0 1 74 1.5 2200 63.7 0.0487 2.0 69.1 2.7 300-305 105 2.5 1 33 1.2 2600 32.6 0.0725 4.0 82.2 - The preferred embodiments of the present invention have been found to be particularly advantageous in that they provide for improved selectivity In addition. they provide a more economic method for converting aromatic carboxylic acids to phenols. This advantage derives from:
(1) Lower cost reactor system (vapour phase vs. liquid phase molten salt reactor).
(2) Elimination of a difficult to dispose of waste stream. The conventional process must draw off a slip stream from the molten mass to maintain catalyst activity. This slip stream contains heavy metals and organics which cannot be simply incinerated for disposal.
(3) Waste heat recovery. The reaction is highly exothermic. The vapour phase reaction is conducted in a temperature range approximately 100"C higher than the liquid phase reaction, making it possible to recover the heat of reaction (e.g., as high pressure steam) at a more efficient temperature level.
(4) The potential for higher yields when producing alkyl-substituted phenols (e.g. cresols). These are less volatile than phenol and, therefore, are more difficult to strip out of a liquid phase. It is well known that if the phenols are not removed from the liquid phase, they will further react and ultimately produce tars.
Claims (10)
1. A process for catalytically oxidising an aromatic carboxylic acid, being benzoic acid or an alkyl-substituted benzoic acid, to the corresponding phenol, the process comprising the steps of: contacting said aromatic carboxylic acid with oxygen and steam in the presence of a catalyst at a temperature of from 200"C to 400"C and at a pressure of from 2 to 20 atmospheres, with an oxygen to carboxyl group mole ratio of from 0.2:1 to 10:1, and a steam to carboxyl group mole ratio of from 5:1 to 500:1, said catalyst comprising copper, zirconium and an alkali metal all in an oxidised state wherein the copper: zirconium: alkali metal atomic ratio is from 1:0.2 to 0.5:0.5 to 2.5.
2. A process according to claim 1 wherein the catalyst comprises a support having a surface area of no greater than 50 m2/g.
3. A process according to claim 2, wherein the support is a-alumina.
4. A process according to any one of the preceding claims wherein the alkali metal is sodium.
5. A process according to any one of claims I to 3 wherein the alkali metal is potassium.
6. A process according to any one of claims 1 to 3 wherein the alkali metal is lithium.
7. A process according to any one of the preceding claims wherein the aromatic carboxylic acid is an alkyl-substituted benzoic acid, the product being a cresol.
8. A process according to any one of claims I to 6 wherein the aromatic carboxylic acid is benzoic acid, the product being phenol.
9. A process according to claim I and substantially as herein described in
Example II.
10. A phenol when made by a process according to any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85304077A | 1977-11-21 | 1977-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1602669A true GB1602669A (en) | 1981-11-11 |
Family
ID=25314866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB24190/78A Expired GB1602669A (en) | 1977-11-21 | 1978-05-30 | Production of phenols |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5920384B2 (en) |
| AU (1) | AU520114B2 (en) |
| CA (1) | CA1098888A (en) |
| DE (1) | DE2844195C2 (en) |
| FI (1) | FI64751C (en) |
| FR (1) | FR2409086A1 (en) |
| GB (1) | GB1602669A (en) |
| IT (1) | IT1106056B (en) |
| NL (1) | NL7810528A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3165748D1 (en) * | 1980-05-16 | 1984-10-04 | Stamicarbon | Method for the preparation of substituted or unsubstituted phenol and catalysts therefor |
| US4390736A (en) * | 1980-11-26 | 1983-06-28 | Sumitomo Chemical Company, Limited | Process for producing phenols |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES291802A1 (en) * | 1962-09-21 | 1964-03-01 | Shell International Res Maatschappij N V | Procedure for converting aromatic carbºxilic acids in phenolic compounds (Machine-translation by Google Translate, not legally binding) |
-
1978
- 1978-05-30 GB GB24190/78A patent/GB1602669A/en not_active Expired
- 1978-09-13 CA CA311,277A patent/CA1098888A/en not_active Expired
- 1978-09-18 AU AU39929/78A patent/AU520114B2/en not_active Expired
- 1978-10-11 DE DE2844195A patent/DE2844195C2/en not_active Expired
- 1978-10-11 JP JP53125016A patent/JPS5920384B2/en not_active Expired
- 1978-10-20 NL NL7810528A patent/NL7810528A/en not_active Application Discontinuation
- 1978-10-26 FI FI783262A patent/FI64751C/en not_active IP Right Cessation
- 1978-11-03 IT IT51770/78A patent/IT1106056B/en active
- 1978-11-15 FR FR7832229A patent/FR2409086A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT1106056B (en) | 1985-11-11 |
| DE2844195A1 (en) | 1979-05-23 |
| AU520114B2 (en) | 1982-01-14 |
| NL7810528A (en) | 1979-05-23 |
| FR2409086B3 (en) | 1981-09-04 |
| FI64751B (en) | 1983-09-30 |
| IT7851770A0 (en) | 1978-11-03 |
| DE2844195C2 (en) | 1985-02-14 |
| JPS5920384B2 (en) | 1984-05-12 |
| JPS5472789A (en) | 1979-06-11 |
| FR2409086A1 (en) | 1979-06-15 |
| FI783262A (en) | 1979-05-22 |
| FI64751C (en) | 1984-01-10 |
| AU3992978A (en) | 1980-03-27 |
| CA1098888A (en) | 1981-04-07 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |