IL45978A - Production of spongy ceramic catalyst supports - Google Patents
Production of spongy ceramic catalyst supportsInfo
- Publication number
- IL45978A IL45978A IL45978A IL4597874A IL45978A IL 45978 A IL45978 A IL 45978A IL 45978 A IL45978 A IL 45978A IL 4597874 A IL4597874 A IL 4597874A IL 45978 A IL45978 A IL 45978A
- Authority
- IL
- Israel
- Prior art keywords
- spheroids
- polystyrene
- ceramic material
- spheroskeleton
- ceramic
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims description 14
- 239000000919 ceramic Substances 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000004793 Polystyrene Substances 0.000 claims description 31
- 229920002223 polystyrene Polymers 0.000 claims description 31
- 229910010293 ceramic material Inorganic materials 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000007900 aqueous suspension Substances 0.000 claims description 9
- 229920006248 expandable polystyrene Polymers 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 238000005202 decontamination Methods 0.000 claims description 4
- 230000003588 decontaminative effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 3
- 229910000278 bentonite Inorganic materials 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 239000012876 carrier material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 235000012907 honey Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0221—Coating of particles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Description
45978/3 r\ PRODUCTION OF SPONQY CERAMIC CATALYST SUPPORTS The present invention relates to the production of spongy ceramic carrier material supporting catalysts which are used in the decontamination of motor exhaust gas, wherein loosely aggregated polystyrene spheroids are joined together across their contact surfaces to a spheroskeleton and the hollow spaces in the spheroskeleton are completely filled with an aqueous suspension of ceramic material.
To initiate a chemical reaction, it is necessary for a catalyst to be heated to a temperature higher than its so-called starting temperature. In the catalytic decontamination of motor exhaust gas, it is customary for the catalyst to be heated up to starting temperature by means of the sensible heat inherent to the exhaust gas. On the other hand, it is known that a cold motor just started produces very noxious exhaust gas. It is therefore highly desirable for the total quantity of catalyst and carrier, which is to be heated up, to be minimized by applying the catalytically active substance to a mirumum quantity of ceramic carrier material.
Attempts have already been made to achieve this with the use of filler catalysts, such as saddles or rings. As described in German Patent Specification 1 278 411, catalysts or catalyst carriers consisting of hollow spheroids have a very low apparent density. Filler catalysts are, however, not fully satisfactory and should conveniently not be used for the decontamination of motor exhaust as. More articularl the are ■ A subject to strong abrasion phenomena due to mechanical 'M-vibration which is caused by motoring and by the pulsating exhaust gas.
As described in German Patent Specifications 1 097 344 and 1 187 535, it is possible to avoid the phenomenon of abrasion by the use of honey comb-structured carrier material having the active substance applied to long parallel passageways through which the exhaust gas is forced to flow. This is not fully satisfactory, however, as the passageways do not provide for the direction of flow of the gas to be inversed therein and do substantially not provide for turbulent gas flow therethrough. In other words, it is very difficult to achieve complete conversion of the gas.
The present invention now provides a process for making a satisfactory abrasionproof catalyst carrier, which enables turbulent gas flow and effective gas conversion in contact with the catalytically active substance.
The process of the present invention comprises more particularly: using hollow spheroids of foamed polystyrene; connecting the individual spheroids together form to /a spheroskeleton by plasticizing their surface areas; filling the hollowspaces left in the spheroskeleton with an aqueous suspension of ceramic material and drying the skeleton at temperatures within the range 20 and 95°C, preferably 40 and 85°C; removing the polystyrene spheroids from the dried material and calcining the ceramic skeleton at temperatures within the range 1000 and 1500°C.
Further preferred features of the present process provide: a) for the surface area of the polystyrene spheroids to be plasticized by treatment with an organic solvent; b) for the surface of. the polystyrene spheroids to be ri ng plasticized by heat^e-d them; c) for the flowability of the suspension of ceramic material to be improved by adding a non-ionic dis- persant thereto; d) for the dispersant to be used in a proportion of 1 weight^; e) for the aqueous suspension of ceramic material to contain up to about 80 weight^ of solid material; f) for fine particulate aluminum oxide to be used as the ceramic material; g) for a mixture of aluminum hydroxide and bentonite to be used as the ceramic material; h) for the polystyrene spheroids to be removed from the dried material by fusion; i) for the polystyrene spheroids to be removed from the dried material by depolymerization; j) for the polystyrene spheroids to be remo\red from the dried material by oxidation; and k) for the polystyrene spheroids to be extracted from the dried material by means of an organic solvent.
"Foamed" polystyrene can be made by heating polystyrene having an expanding agent, e.g. n-pentane, dissolved therein. On heating, the expanding agent is evaporated and the polystyrene expanded approximately to 50 times its initial volume. '9f' By treatment with an organic solvent, e.g. acetone, or by heat treatment, the surface areas of the polystyrene are plasticized and deformed. As a result, the loosely aggregated polystyrene spheroids, which, initially communicate with each other through contact points, are connected together through contact surfaces leaving the hollov; spaces between the individual spheroids unaffected.
Once the expanding agent has been expelled completely, it is impossible for foamed polystyrene spheroids to. be further expanded. They collapse, even if heating is continued. This however is desirable with respect to the spheroskeleton and with respect to the ceramic filler material occupying the hollow spaces therein. In . other words, it is possible for the ceramic filler to be heated and to be kept free from cracking phenomena which in the end effect break-up of the ceramic skeleton. Unfoamed polystyrene and other plastics, which un-dergo considerably more thermal expansion than ceramic material, have been found to be subject to cracking.
The spongy ceramic material of the present invention represents some sort of a negative aggregation of spheroidal particles. This is aggregated material, wherein hollow spaces replace the spheroids and ceramic v/alls replace the interspaces left between the individual spheroids. The hollow spaces which communicate with each other enable gas to travel therethrough from one hollow space to the neighboring hollow spaces, while the direction of gas flow is continually inversed.
In other words, the spongy ceramic material of the present invention combines the valuable properties of a filler catalyst with those of a honey comb-structured catalyst. It has as low an apparent density as hollow spheroids, for example, and opposes as little resistance to flowing gas as honey comb structures. In addition thereto, it enables the gas to be passed therethrough in turbulent flow and to. be completely transformed in contact with the catalytically active substance.
The following Examples illustrate the invention: EXAMPLE 1 : Spheroidal polystyrene particles containing dissolved n-pentane were sieved and a sieve fraction of particles having a diameter between 0.1 and 0.2 mm was placed in a drying cabinet, left therein for 30 minutes at 135°C, and foamed polystyrene ;vas obtained.
The foamed polystyrene spheroids were sieved and a sieve fraction of particles having a diameter between 1 and 1.5 mm was placed in a glass cylinder closed at one of its ends, which was 25 mm in diameter, 100 mm high and slightly shaken.
Following this, an acetone/water-mixture (20 weighty of water) was poured over the spheroids in the glass cylinder, which were completely covered with liquid. This effected superficial dissolution and agglutination of the individual spheroids. This was stopped after 3 minutes. The liquid was poured off and the spheroskeleton so obtained was dried at room tempera- An aqueous suspension of fine particulate, highly reactive aluminum oxide ("Activated alumina" A 16) which contained 80 % of solid matter and 1 % of a non-ionic dispersant to improve flowability (DOLAPIX CA, a product of Zschimmer and Schwarz, Lahnstein) , was forced through the agglutinated polystyrene spheroids, by means of an extruder. The spheroskeleton so charged with aluminum oxide was taken from the glass cylinder and dried for 12 hours at room temperature.
The polystyrene spheroids were oxidized and/or depolymerized. To this end, the dried material was heated to 450°C at a temperature increase of 50°C per hour.
Following this, the material was heated to 1450°C at a temperature increase of 250°C per hour, and maintained at that temperature for 4 hours.
The resulting spongy ceramic material had a diameter of 21.5 mm, a length of 85 mm and a weight of 21 g. This corresponded to an apparent density of 0.68 cc/g.
EXAMPLE 2: 0.6 g of blowable polystyrene spheroids, which were placed in a drying cabinet and allowed to foam therein for 20 minutes at 135°C, were sieved in the manner described in Example -and placed in a glass cylinder. Hot air was injected thereinto at 135°C and an agglutinated cylindrical shape 24 mm in diameter and 70 mm high was obtained.
The cylindrical shape so obtained was dipped in an aqueous suspension of fine particulate, highly reactive aluminum oxide ("Activated alumina" A 16) which The suspension was in a vibrating container. After approximately 5 minutes, the cylindrical shape W_B completely impregnated with the ceramic suspension .
Suspension residues which adhered to the exterior of the shape were wiped off or scraped off and the sphero skeleton filled with aluminum oxide was dried initially for 2 hours at 40°C and later for 1 hour at 85°C.
The polystyrene spheroids were oxidized and/or depolymerized and the ceramic skeleton was calcined in the manner described in Example 1.
The resulting spongy ceramic material had ;a diameter of 20 mm, a length of 60 mm and a weight of 13 g This corresponded to an apparent density of 0.72 cc/g.
EXAMPLE 3: 0.6 g of blowable polystyrene spheroids were plac ed in a drying cabinet and allowed to foam therein for 30 minutes at 35°C. A sieve fraction consisting of particles with a diameter of more than 1 mm was placed in a glass cylinder and the individual particles were form connected together to /a spheroskeleton.
The spheroskeleton so obtained was filled with ceramic material and dried, in the manner described in Example .
The dry material was dipped for 30 minutes in acetone. This effected complete dissolution of the polystyrene spheroids, ft is also satisfactory, however, to merely effect collapse of the polystyrene spheroids, by dipping the dry material, in acetone for 1 minute. Polystyrene, which may be retained in the interior of the spheroskeleton, is then burnt durin calcination. This was effected in .the manner described in Example .
The spongy ceramic material so made had a density of 0.59 cc/g.
EXAMPLE : A spheroskeleton of foamed polystyrene spheroids was prepared in the manner described in Example .
An aqueous suspension containing 77 % of solid matter was prepared from a mixture of 90 weight% of a-Al(OH)^ (Martifin, a product of Martinswerk GmbH, Bergheim) and 10 welght% of bentonite (a product of Erbsloh, Geisenheim) . After the addition, of 1 % of DOLAPIX CA, the suspension had a viscosity low enough to permit penetration under vibration into the hollow spaces of the spheroskeleton of foamed polystyrene spheroids .
The spheroskeleton filled with ceramic material was dried and calcined in the manner described in Example 1 , and spongy ceramic material which had an apparent density of 0.62 cc/g was obtained.
Claims (12)
1. . A process for making spongy ceramic material supporting catalysts which are used in t ie decontamination of motor exhaust gas , wherein loosely aggregated polystyrene spheroids are joined together across thei r contact surfaces to form a spheroskeleton and the hol low spaces in the spheroskeleton are completely filled with an aqueous suspension of ceramic material , which process comprises using hollow spheroids of foamed polystyrene; connecting the individual spheroi ds together to form a spheroskeleton by pl asti c! zing thei r surface areas ; fi lling the hollow spaces left in the spherosYkeleton with the aqueous suspension of ceramic material selected from the group consisting of aluminum oxide , al uminum hydroxide, bentonite or mixtures thereof, and drying the skeleton at temperatures within the range 20 and 95°C, preferably 40 and 85°C ; removing the polystyrene spheroids from the dried material and calcining the ceramic skeleton at temperatures within the range 1000 and 1500°C.
2. A process as cl aimed in claim 1 , wherein the surface area of the polystyrene spheroids is plasticized by treatment with an organic sol vent.
3. A process as claimed in claim 1 , wherein the surface area of the polystyrene spheroids is plasticized by heating.
4. A process as claimed in any one of claims 1 to 3, wherein the flowabi lity of the suspension of ceramic material is improved by adding a non-ioni c dispersant thereto.
5. A process as claimed in cl aim 4, wherein the dispersant is used in a proportion of 1 weight%. 45978/2
6. A process as claimed in any one of claims 1 to 5, wherein the aqueous suspension of ceramic material contains up to about 80 weight% of solid material. 6
7. A process as claimed in any one of claims 1 to/8f, wherein the polystyrene spheroids are removed from the dried material by fusion.
8. A process as claimed in any one of claims 1 to 6, wherein the polystyrene spheroids are removed from the dried material by depolymeri zati on .
9. A process as claimed in any one of claims 1 to 6, wherein the polystyrene spheroids are removed from the dried material by oxidation.
10. A process as claimed in any one of claims 1 to 6, wherein the polystyrene spheroids are extracted from the dried material by means of an organic solvent.
11. A process for making spongy ceramic material conducted substantially as described in any one of Examples 1 to 4 herein.
12. Spongy ceramic material whenever obtained by a process as claimed in any one of claims 1 to ttorneys or pp cant
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2355498A DE2355498C3 (en) | 1973-11-07 | 1973-11-07 | Method of manufacturing a sponge-like ceramic body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IL45978A0 IL45978A0 (en) | 1975-02-10 |
| IL45978A true IL45978A (en) | 1977-05-31 |
Family
ID=5897351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IL45978A IL45978A (en) | 1973-11-07 | 1974-11-01 | Production of spongy ceramic catalyst supports |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5075608A (en) |
| AT (1) | AT344669B (en) |
| BE (1) | BE821896A (en) |
| BR (1) | BR7409283A (en) |
| CA (1) | CA1039480A (en) |
| CH (1) | CH606780A5 (en) |
| DD (1) | DD117616A5 (en) |
| DE (1) | DE2355498C3 (en) |
| DK (1) | DK579074A (en) |
| FR (1) | FR2249851B1 (en) |
| GB (1) | GB1462237A (en) |
| IL (1) | IL45978A (en) |
| IT (1) | IT1023138B (en) |
| NL (1) | NL7414361A (en) |
| PL (1) | PL97181B1 (en) |
| RO (1) | RO71032A (en) |
| SE (1) | SE7413935L (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60251182A (en) * | 1984-05-28 | 1985-12-11 | 品川白煉瓦株式会社 | Manufacture of porous refractory solid |
| DE3511825A1 (en) * | 1985-03-30 | 1986-10-02 | Feldmühle AG, 4000 Düsseldorf | Sintered article of ceramic material |
| JPH0631179B2 (en) * | 1985-10-18 | 1994-04-27 | マツダ株式会社 | Method for manufacturing filter for purifying exhaust gas of engine |
| JP2759147B2 (en) * | 1987-02-25 | 1998-05-28 | 住友化学工業株式会社 | Method for producing porous ceramic body |
| DE3724156A1 (en) * | 1987-07-22 | 1989-02-02 | Norddeutsche Affinerie | METHOD FOR PRODUCING METALLIC OR CERAMIC HOLLOW BALLS |
| DE3729126A1 (en) * | 1987-09-01 | 1989-04-06 | Mototech Motoren Umweltschutz | Diesel soot-particle filter and process for the production thereof |
| JPH05310464A (en) * | 1992-05-11 | 1993-11-22 | Kunnetsupu Sekkai Kogyo Kk | Spherical shell-shaped heat insulating material and its production |
| DE4420839A1 (en) * | 1994-06-15 | 1995-12-21 | Steag Ag | Method and device for separating vaporous alkali and heavy metal compounds from hot combustion gases |
-
1973
- 1973-11-07 DE DE2355498A patent/DE2355498C3/en not_active Expired
-
1974
- 1974-10-07 CH CH1343574A patent/CH606780A5/xx not_active IP Right Cessation
- 1974-10-28 GB GB4645774A patent/GB1462237A/en not_active Expired
- 1974-10-31 JP JP49126059A patent/JPS5075608A/ja active Pending
- 1974-10-31 IT IT53831/74A patent/IT1023138B/en active
- 1974-11-01 IL IL45978A patent/IL45978A/en unknown
- 1974-11-04 NL NL7414361A patent/NL7414361A/en not_active Application Discontinuation
- 1974-11-05 AT AT885874A patent/AT344669B/en not_active IP Right Cessation
- 1974-11-05 DD DD182157A patent/DD117616A5/xx unknown
- 1974-11-06 DK DK579074A patent/DK579074A/da unknown
- 1974-11-06 SE SE7413935A patent/SE7413935L/xx unknown
- 1974-11-06 PL PL1974175618A patent/PL97181B1/en unknown
- 1974-11-06 RO RO7480440A patent/RO71032A/en unknown
- 1974-11-06 CA CA213,181A patent/CA1039480A/en not_active Expired
- 1974-11-06 BR BR9283/74A patent/BR7409283A/en unknown
- 1974-11-06 BE BE150250A patent/BE821896A/en unknown
- 1974-11-07 FR FR7436930A patent/FR2249851B1/fr not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| NL7414361A (en) | 1975-05-12 |
| DE2355498C3 (en) | 1979-08-30 |
| RO71032A (en) | 1981-11-24 |
| BR7409283A (en) | 1976-05-11 |
| DD117616A5 (en) | 1976-01-20 |
| PL97181B1 (en) | 1978-02-28 |
| DE2355498A1 (en) | 1975-06-05 |
| CA1039480A (en) | 1978-10-03 |
| GB1462237A (en) | 1977-01-19 |
| DE2355498B2 (en) | 1979-01-11 |
| FR2249851A1 (en) | 1975-05-30 |
| CH606780A5 (en) | 1978-11-15 |
| BE821896A (en) | 1975-05-06 |
| FR2249851B1 (en) | 1980-12-05 |
| AT344669B (en) | 1978-08-10 |
| DK579074A (en) | 1975-07-14 |
| SE7413935L (en) | 1975-05-09 |
| JPS5075608A (en) | 1975-06-20 |
| ATA885874A (en) | 1977-12-15 |
| IL45978A0 (en) | 1975-02-10 |
| IT1023138B (en) | 1978-05-10 |
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