EP0000564B1 - 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 Download PDFInfo
- Publication number
- EP0000564B1 EP0000564B1 EP78100469A EP78100469A EP0000564B1 EP 0000564 B1 EP0000564 B1 EP 0000564B1 EP 78100469 A EP78100469 A EP 78100469A EP 78100469 A EP78100469 A EP 78100469A EP 0000564 B1 EP0000564 B1 EP 0000564B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalysts
- mixtures
- catalyst
- acrylonitrile
- methacrylonitrile
- 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
- 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
Definitions
- the catalysts of the present invention may be used unsupported or supported on various conventional carriers such as Si0 2 , AI 2 0 3 , Zr0 2 , Ti0 2 , BP0 4 , SbP0 4 , 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.
Description
- 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.
- Catalysts for the oxidation, ammoxidation and oxydehydrogenation of olefins are well known. See, for example, U.S. 3,642,930 and U.S. 3,414,631, the disclosures of which are incorporated herein by reference. Further note commonly assigned US-applications Serial No. 490,532 filed July 22, 1974, Serial No. 380,527 filed July 19, 1973, and Serial No. 717,838 filed August 26, 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.
- The present invention is based on the discovery that certain oxidation 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.
-
- 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 Bi or Te; and
- 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;
- 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 contains the above-indicated 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 particularly preferred embodiment, the foregoing preferred and optimal catalysts contain K, Rb 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 Z component is selected from the following combinations of elements 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 Si02, AI203, Zr02, Ti02, BP04, 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 which are conventional.
-
- A solution of 127.1 g ammonium heptamolybdate (NH4)6Mo7O24 . 4H2O and water was prepared. To this solution was added 6.9 g of a 42.5% solution of H3P04 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 . 9H20; 29.1 g bismuth nitrate, Bi(NO3)3. 5H2O: 78.6 g cobalt nitrate Co(NO3)2. 6H2O; 43.6 g nickel nitrate Ni(NO3)2. 6H2O: and 6.1 g of a 10% potassium nitrate solution was prepared. The solution of metal nitrates was slowly added to the slurry. The resulting slurry was evaporated to dryness, and the solid obtained was heat treated at 290°C for three hours, at 425°C for three hours and at 550°C for 16 hours.
- In the same manner as discussed in Comparative Example A, catalysts listed in the following Table I 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 was set forth in the following Table I.
- The parentheses used in Table I as well as the following Table II have no significance other than to clarify the difference between the various catalysts.
- 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% Si02. The results obtained are set forth in the following Table II.
wherein
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.
Claims (7)
wherein
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.
wherein
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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US81973277A | 1977-07-28 | 1977-07-28 | |
US819732 | 1977-07-28 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000564A1 EP0000564A1 (en) | 1979-02-07 |
EP0000564B1 true EP0000564B1 (en) | 1982-05-19 |
Family
ID=25228901
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100469A Expired EP0000564B1 (en) | 1977-07-28 | 1978-07-21 | Catalysts containing iron and molybdenum and the use of these catalysts in the preparation of acrylonitrile or methacrylonitrile |
Country Status (20)
Country | Link |
---|---|
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) |
DK (1) | DK333778A (en) |
EG (1) | EG13970A (en) |
ES (1) | ES471682A1 (en) |
FI (1) | FI66129C (en) |
GR (1) | GR66444B (en) |
IE (1) | IE47301B1 (en) |
IL (1) | IL55073A (en) |
IN (1) | IN148019B (en) |
IT (1) | IT1196394B (en) |
NO (1) | NO150345C (en) |
PT (1) | PT68312A (en) |
RO (1) | RO77761A (en) |
ZA (1) | ZA783914B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1127137A (en) * | 1977-12-20 | 1982-07-06 | Dev D. Suresh | Ammoxidation of olefins with novel antimonate catalysts |
US4316855A (en) * | 1979-12-28 | 1982-02-23 | The Standard Oil Co. | Multiply promoted Sn-Sb oxide catalysts |
ATE7861T1 (en) * | 1980-07-18 | 1984-06-15 | Mitsubishi Chemical Industries Limited | CATALYTIC COMPOSITION, PROCESS FOR ITS PREPARATION AND ITS USE. |
ATE34090T1 (en) * | 1982-09-30 | 1988-05-15 | Monsanto Co | CATALYSTS FOR THE OXIDATION AND AMMOXIDATION OF ALCOHOLS. |
US4469810A (en) * | 1983-01-11 | 1984-09-04 | Mitsubishi Rayon Company Limited | Process for the calcination of phosphorus-molybdenum catalyst |
GB2221852A (en) * | 1988-08-18 | 1990-02-21 | Ti Corporate Services | Vehicle exhaust gas catalysts |
US5093299A (en) * | 1990-01-09 | 1992-03-03 | The Standard Oil Company | Catalyst for process for the manufacture of acrylonitrile and methacrylonitrile |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5112603B1 (en) * | 1971-05-26 | 1976-04-21 | ||
CA1004232A (en) * | 1971-12-30 | 1977-01-25 | The Standard Oil Company | Coproduction of methacrylonitrile and butadiene |
CA1049553A (en) * | 1973-04-30 | 1979-02-27 | The Standard Oil Company | Preparation of acrylic acid and methacrylic acid from propylene or isobutylene in a one-reactor, fluid-bed system |
FR2228538B1 (en) * | 1973-05-10 | 1977-06-24 | Japan Synthetic Rubber Co Ltd | |
DE2424934A1 (en) * | 1973-06-04 | 1975-01-02 | Standard Oil Co Ohio | METHOD OF CATALYTIC PRODUCTION OF UNSATATULATED NITRILES |
US3972920A (en) * | 1973-06-11 | 1976-08-03 | Mitsubishi Rayon Co., Ltd. | Process for producing unsaturated aldehydes, unsaturated fatty acids or conjugated dienes |
DE2428218A1 (en) * | 1973-06-15 | 1975-01-09 | Forni Ed Impianti Ind Ingg De | METHODS FOR TREATMENT OF WASTE, IN PARTICULAR FROM MUELL |
US3883573A (en) * | 1973-06-15 | 1975-05-13 | Standard Oil Co | Commercial fixed-bed acrylonitrile or methacrylonitrile |
US3932551A (en) * | 1973-10-12 | 1976-01-13 | The Standard Oil Company | Process for the preparation of diolefins from olefins |
GB1523772A (en) * | 1974-07-22 | 1978-09-06 | Standard Oil Co | Oxidation catalysts |
US4001317A (en) * | 1974-07-22 | 1977-01-04 | Standard Oil Company | Process for the oxidation of olefins using catalysts containing various promoter elements |
GB1489559A (en) * | 1975-03-03 | 1977-10-19 | Mitsubishi Rayon Co | Catalytic process for the preparation of acrylic acid or methacrylic acid |
GB1490683A (en) * | 1975-03-12 | 1977-11-02 | Mitsubishi Rayon Co | Process and a catalyst for producing unsaturated aldehydes unsaturated carboxylic acids or conjugated diene |
IN142430B (en) * | 1975-04-21 | 1977-07-09 | Standard Oil Co | |
US4118419A (en) * | 1975-12-03 | 1978-10-03 | Mitsubishi Rayon Company, Ltd. | Catalytic process for the preparation of an unsaturated carboxylic acid |
DE2626887B2 (en) * | 1976-06-16 | 1978-06-29 | Basf Ag, 6700 Ludwigshafen | Catalyst for the oxadation of (methacrolein to (meth) acrylic acid |
US4335264A (en) * | 1976-07-07 | 1982-06-15 | E. I. Du Pont De Nemours And Company | High yield, low byproduct α, β-unsaturated aldehydes from olefins |
US4065507A (en) * | 1976-08-02 | 1977-12-27 | Standard Oil Company | Preparation of methacrylic derivatives from tertiary butyl-containing compounds |
-
1978
- 1978-07-04 IL IL55073A patent/IL55073A/en unknown
- 1978-07-05 GR GR56696A patent/GR66444B/el unknown
- 1978-07-05 CA CA306,799A patent/CA1132124A/en not_active Expired
- 1978-07-07 ZA ZA00783914A patent/ZA783914B/en unknown
- 1978-07-07 IN IN507/DEL/78A patent/IN148019B/en unknown
- 1978-07-11 AU AU37930/78A patent/AU525163B2/en not_active Expired
- 1978-07-13 ES ES471682A patent/ES471682A1/en not_active Expired
- 1978-07-18 PT PT68312A patent/PT68312A/en unknown
- 1978-07-19 FI FI782285A patent/FI66129C/en not_active IP Right Cessation
- 1978-07-21 EP EP78100469A patent/EP0000564B1/en not_active Expired
- 1978-07-21 DE DE7878100469T patent/DE2861849D1/en not_active Expired
- 1978-07-25 DD DD78206917A patent/DD137532A5/en unknown
- 1978-07-26 EG EG459/78A patent/EG13970A/en active
- 1978-07-26 IT IT26142/78A patent/IT1196394B/en active
- 1978-07-26 DK DK333778A patent/DK333778A/en not_active Application Discontinuation
- 1978-07-27 BR BR7804847A patent/BR7804847A/en unknown
- 1978-07-27 IE IE1523/78A patent/IE47301B1/en unknown
- 1978-07-27 RO RO7894814A patent/RO77761A/en unknown
- 1978-07-27 NO NO782582A patent/NO150345C/en unknown
- 1978-07-27 AT AT0547778A patent/AT363911B/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
IT1196394B (en) | 1988-11-16 |
AU3793078A (en) | 1980-01-17 |
CA1132124A (en) | 1982-09-21 |
IE47301B1 (en) | 1984-02-22 |
NO150345B (en) | 1984-06-25 |
DE2861849D1 (en) | 1982-07-08 |
AT363911B (en) | 1981-09-10 |
DK333778A (en) | 1979-01-29 |
RO77761A (en) | 1981-11-24 |
AU525163B2 (en) | 1982-10-21 |
GR66444B (en) | 1981-03-23 |
PT68312A (en) | 1978-08-01 |
DD137532A5 (en) | 1979-09-12 |
FI66129B (en) | 1984-05-31 |
FI66129C (en) | 1984-09-10 |
NO150345C (en) | 1984-10-03 |
IT7826142A0 (en) | 1978-07-26 |
EG13970A (en) | 1983-03-31 |
ES471682A1 (en) | 1979-10-01 |
BR7804847A (en) | 1979-04-10 |
ATA547778A (en) | 1981-02-15 |
IE781523L (en) | 1979-01-28 |
NO782582L (en) | 1979-01-30 |
IN148019B (en) | 1980-09-27 |
IL55073A (en) | 1982-01-31 |
EP0000564A1 (en) | 1979-02-07 |
FI782285A (en) | 1979-01-29 |
ZA783914B (en) | 1979-08-29 |
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