CA1046535A - Process for the hydrogenation of diolefin hydrocarbons to olefin hydrocarbons - Google Patents
Process for the hydrogenation of diolefin hydrocarbons to olefin hydrocarbonsInfo
- Publication number
- CA1046535A CA1046535A CA177,367A CA177367A CA1046535A CA 1046535 A CA1046535 A CA 1046535A CA 177367 A CA177367 A CA 177367A CA 1046535 A CA1046535 A CA 1046535A
- Authority
- CA
- Canada
- Prior art keywords
- diolefin
- hydrocarbons
- reaction
- hydrogenation
- process according
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/44—Palladium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/053—Sulfates or other compounds comprising the anion (SnO3n+1)2-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/138—Compounds comprising a halogen and an alkaline earth metal, magnesium, beryllium, zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
- C07C2527/25—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The disclosure relates to the selective hydrogenation of diolefin hydrocarbons to form olefin hydrocarbons, said hydrogenation being carried out in the presence of a palladium base catalyst. Selectivity is as close as possible to 100%
if an aqueous zinc solution is added to the diolefin hydrocarbon which is to be hydrogenated.
The disclosure relates to the selective hydrogenation of diolefin hydrocarbons to form olefin hydrocarbons, said hydrogenation being carried out in the presence of a palladium base catalyst. Selectivity is as close as possible to 100%
if an aqueous zinc solution is added to the diolefin hydrocarbon which is to be hydrogenated.
Description
~ 3 5 '~'he ~re~ent invention rela-tes to a process ~or the select.ive hydrogena-tion of diolefin hydrocarbons -to ~orm ole~in hydrocarbons It is already known that it is possible to hydrogenate diole~in compounds in the presence of palladium catalystO However in all these cases a mixture o~ ole~in and saturated oompounds is obtained with an uncontrolled selectively o~ the olefin :~
compounasO
To reach satls~actory results and to stop the subsequent hydrogenation o~ the olefin compound into a saturated compound9 it has been proposed to partially deactivate the palladium ;-catalyst7 by impregnation or coprecipitation Y~ith salts of Pb, .
. -:, , - .
~ Zn~ Hg, Cd, '~ht Sn, etc~
Howevex said impregnation or coprecipi-tation methods -~
aro di~ficul-t to be carried out in practice, because the de-activation conditions o~ the catalyst (temperature, deactivating ~alt concentration, operating time) are very critical; as a matter o~ ~act, by operating under conditions which are only slightly di~erent ~rom those which are optimum9 there are obtained :.
20 catalysts ~hich are either non selective or ~holly deactivated. .
It is also known that in order to obtain high selectivity catalyst it is necessary that the impregnatio~ or coprecipitation ~.
treatment be carrled out at a rather elevated temperature ( 80 to 1000a)~ which, on the other ha~d, is particularly di~advantageous in the case of supported catalysts.
We have now ~ound that it is possible to obtain selec- ~:
tivity as close a~ 100%9 in the hydrogenation o~ diole~in ~
oompounds to ~orm ole~in compounds, by operating at relatively : ~ -low temperature or in any case at a temperature ranging from 20C
to 60oa, by employing conventional palladium catalysts, possibly supported ~or insta~ce on calcium carbonate or barium sul~ate a~d by adding an aqueous solution of zinc salt to the reaction mi.xtuxe~
-- - . . - .
.: -' ' . ': ' .
3 5 ' Therefore~ by opera-ting according to -the present invention it is possible -to obtain selectivities as high as 100% wi-thou-t ha~-i~g to subject the palladium catalys-t to the hot impregnating or coprecipita-ti,ng operations which are very expensive and complicated9 because the zinc is added oontinuously as an aqueous solution to the hydrogenation mixtureO Beside the above practical and economical adva~tage9 the presen-t invention represents a *ur-ther progress in that the li~e of the catalyst employed accord-ing -to the invention~ at same selectivity values, is longer than 1o the li~e o~ the known deactivated catalysts According to the present invention the passage of material to be hydrogena-ted and zinc salt over the catalyst in , the course o~ the continuous tests can be a~fected ma~y times Y~hile ~ ' always obtaining very good selectivityO The anion o-~ the zinc salt has no importance as to the selecti~ity9 however it is , -preferable that the salt have a high solubility in waterO In this connection the chloride, sulfate7 nitrate, acetate and oxala~e are quite suitable~ ' ' ' ~' ?he amount o~ salt can ~ary ~rom OoOl to 5% and pre~era-bly ~rom 0.01 to 2% by weight with respect -to the diolefin oompoundO
~ he minlmum amount o~ water necessary for a good reaction course should be enough to dissolve the ~inc salt undex the reaction condition~
It is there~ore necessary to have a ratio water/zinc ,-salt at least of 1/1 by weight.
On the other hand it is ad~isable to u-tilize a wa-ter/
zinc salt ratio w~lich is not higher than 50/1 in order to ha~e a satisfactory reaction rate.
In the absence o~ water the hydrogenation o~ t~e diole~in compounds i,s not stopped at the 1st stage~ i~e~ at the ~ormation o~ the ole~in compounds, but it goes on -till saturated compoun~s :
~, ' ' , ~ O~S 3 S
are produced~ It i.s pre~erable to add an amino compound to the reaction mix-ture generally ammonia, in very low amount.s, pre~erably lower than 0,5% by weight vrith respect to the diole~in compound, even i-~ higher amounts9 u~ to 20 to 30% do not adversely e~ect the reactionO
The present invention can be applied to continuous or discontinuous prooesses in a wide range o~ temperature~ for instance between 20C and 60C, and o~ pressure~ Por ins-tance from 1 to 50 absolute atmospheres~
It is to be noted that the amount of salt which is to be added to the reaction mixture, within the abovementioned ranges, depends on the reaction rate, i~eO on the hydrogen pressure and the temperature, and also on the eE~iciency o~ stirring. ;
By operating according to the present invention, the absorption o~ hydrogen ~rom the reacting ~ixture stops a~ter one oE the double bonds has been hydrogenated into a simple bond;
then, by allowing the reacted mixture to be kept at the reaction conditions ~or relatively long times, no substantial further hydrogenation occurs O ~ .
The prese~t invention will be better illustrated by the ~ollowing operative examples.
EXAMP~?. 1 Cyclopentadiene was hydrogenated in the presence of 2%
by weight of a Pd base catalysts on CaC03 as catalyst carrier (5% Pd) at the temperatures o~ 30C. 0.2% o:E ammonia, 0.2% of dihydrated zinc acetate and o.a,% by weight of water w~re added into an autoclave kept under stirring by means o~ a stirrer consisting o~a hollow shaft ~or allowing a recirculation of hydro~
hydrogen~ '~he hydrogen pressure was 5 kg/cm20 r~he course of the reaction was controlled by gas~
chromatography analysis perEormed on samples drawn at regular ~046535 in te:r ~,r-~ls .
~ -~ter 90 minute,s there was no more hydrogen absorption and the selec-tivity as cyclopentane~
cyclopentane __ _ _ % by moles cyclopentane ~ cyclopentane was 99O4~ ~t the start, cyclopentadiene wa~q practically absent. ~, After other 90 minutes, under the reaction conditions the selec- ~
tively was higher than 99~0. -EX~PIE 2 ~ he process was carried out as in example 1, except that the ~nount of water was 1%. A~ter the starting cyclopenta-diene had di.sappeared9 the selectivity o~ the obtained produc-t as cyclopentene was 99.2% ana it was practically constant also a-~ter a long period o~ time during which the product remained under the reaction conditionsO
~he process was carried out as in example 1, except ~ -that no water was addedn ~he selectivity as cyclopentene, a~ter the disappearance o~ dicyclopentadiene was 89%; by keeping the --product under the reaction conditions ~or another 30 minutes the selectivity decreased to 74% becaus0 o~ the ~ormation o~
cyclopentane and9 a~ter another 30 minutes7 the selectivity decreased to 60%.
EXAMPIæ 4 and 5 .. ~................................................. ~
Isoprene and pentadiene were subjected to hydrogenation according to example 1.
A~ter the total disappearance o~ the diolefins, there were obtained mixtures of ole~ine isomers with selectivities respec-tively o~' 99O1 and 98.7.
`' ., .. ~ :
compounasO
To reach satls~actory results and to stop the subsequent hydrogenation o~ the olefin compound into a saturated compound9 it has been proposed to partially deactivate the palladium ;-catalyst7 by impregnation or coprecipitation Y~ith salts of Pb, .
. -:, , - .
~ Zn~ Hg, Cd, '~ht Sn, etc~
Howevex said impregnation or coprecipi-tation methods -~
aro di~ficul-t to be carried out in practice, because the de-activation conditions o~ the catalyst (temperature, deactivating ~alt concentration, operating time) are very critical; as a matter o~ ~act, by operating under conditions which are only slightly di~erent ~rom those which are optimum9 there are obtained :.
20 catalysts ~hich are either non selective or ~holly deactivated. .
It is also known that in order to obtain high selectivity catalyst it is necessary that the impregnatio~ or coprecipitation ~.
treatment be carrled out at a rather elevated temperature ( 80 to 1000a)~ which, on the other ha~d, is particularly di~advantageous in the case of supported catalysts.
We have now ~ound that it is possible to obtain selec- ~:
tivity as close a~ 100%9 in the hydrogenation o~ diole~in ~
oompounds to ~orm ole~in compounds, by operating at relatively : ~ -low temperature or in any case at a temperature ranging from 20C
to 60oa, by employing conventional palladium catalysts, possibly supported ~or insta~ce on calcium carbonate or barium sul~ate a~d by adding an aqueous solution of zinc salt to the reaction mi.xtuxe~
-- - . . - .
.: -' ' . ': ' .
3 5 ' Therefore~ by opera-ting according to -the present invention it is possible -to obtain selectivities as high as 100% wi-thou-t ha~-i~g to subject the palladium catalys-t to the hot impregnating or coprecipita-ti,ng operations which are very expensive and complicated9 because the zinc is added oontinuously as an aqueous solution to the hydrogenation mixtureO Beside the above practical and economical adva~tage9 the presen-t invention represents a *ur-ther progress in that the li~e of the catalyst employed accord-ing -to the invention~ at same selectivity values, is longer than 1o the li~e o~ the known deactivated catalysts According to the present invention the passage of material to be hydrogena-ted and zinc salt over the catalyst in , the course o~ the continuous tests can be a~fected ma~y times Y~hile ~ ' always obtaining very good selectivityO The anion o-~ the zinc salt has no importance as to the selecti~ity9 however it is , -preferable that the salt have a high solubility in waterO In this connection the chloride, sulfate7 nitrate, acetate and oxala~e are quite suitable~ ' ' ' ~' ?he amount o~ salt can ~ary ~rom OoOl to 5% and pre~era-bly ~rom 0.01 to 2% by weight with respect -to the diolefin oompoundO
~ he minlmum amount o~ water necessary for a good reaction course should be enough to dissolve the ~inc salt undex the reaction condition~
It is there~ore necessary to have a ratio water/zinc ,-salt at least of 1/1 by weight.
On the other hand it is ad~isable to u-tilize a wa-ter/
zinc salt ratio w~lich is not higher than 50/1 in order to ha~e a satisfactory reaction rate.
In the absence o~ water the hydrogenation o~ t~e diole~in compounds i,s not stopped at the 1st stage~ i~e~ at the ~ormation o~ the ole~in compounds, but it goes on -till saturated compoun~s :
~, ' ' , ~ O~S 3 S
are produced~ It i.s pre~erable to add an amino compound to the reaction mix-ture generally ammonia, in very low amount.s, pre~erably lower than 0,5% by weight vrith respect to the diole~in compound, even i-~ higher amounts9 u~ to 20 to 30% do not adversely e~ect the reactionO
The present invention can be applied to continuous or discontinuous prooesses in a wide range o~ temperature~ for instance between 20C and 60C, and o~ pressure~ Por ins-tance from 1 to 50 absolute atmospheres~
It is to be noted that the amount of salt which is to be added to the reaction mixture, within the abovementioned ranges, depends on the reaction rate, i~eO on the hydrogen pressure and the temperature, and also on the eE~iciency o~ stirring. ;
By operating according to the present invention, the absorption o~ hydrogen ~rom the reacting ~ixture stops a~ter one oE the double bonds has been hydrogenated into a simple bond;
then, by allowing the reacted mixture to be kept at the reaction conditions ~or relatively long times, no substantial further hydrogenation occurs O ~ .
The prese~t invention will be better illustrated by the ~ollowing operative examples.
EXAMP~?. 1 Cyclopentadiene was hydrogenated in the presence of 2%
by weight of a Pd base catalysts on CaC03 as catalyst carrier (5% Pd) at the temperatures o~ 30C. 0.2% o:E ammonia, 0.2% of dihydrated zinc acetate and o.a,% by weight of water w~re added into an autoclave kept under stirring by means o~ a stirrer consisting o~a hollow shaft ~or allowing a recirculation of hydro~
hydrogen~ '~he hydrogen pressure was 5 kg/cm20 r~he course of the reaction was controlled by gas~
chromatography analysis perEormed on samples drawn at regular ~046535 in te:r ~,r-~ls .
~ -~ter 90 minute,s there was no more hydrogen absorption and the selec-tivity as cyclopentane~
cyclopentane __ _ _ % by moles cyclopentane ~ cyclopentane was 99O4~ ~t the start, cyclopentadiene wa~q practically absent. ~, After other 90 minutes, under the reaction conditions the selec- ~
tively was higher than 99~0. -EX~PIE 2 ~ he process was carried out as in example 1, except that the ~nount of water was 1%. A~ter the starting cyclopenta-diene had di.sappeared9 the selectivity o~ the obtained produc-t as cyclopentene was 99.2% ana it was practically constant also a-~ter a long period o~ time during which the product remained under the reaction conditionsO
~he process was carried out as in example 1, except ~ -that no water was addedn ~he selectivity as cyclopentene, a~ter the disappearance o~ dicyclopentadiene was 89%; by keeping the --product under the reaction conditions ~or another 30 minutes the selectivity decreased to 74% becaus0 o~ the ~ormation o~
cyclopentane and9 a~ter another 30 minutes7 the selectivity decreased to 60%.
EXAMPIæ 4 and 5 .. ~................................................. ~
Isoprene and pentadiene were subjected to hydrogenation according to example 1.
A~ter the total disappearance o~ the diolefins, there were obtained mixtures of ole~ine isomers with selectivities respec-tively o~' 99O1 and 98.7.
`' ., .. ~ :
Claims (5)
1. In a process for the selective hydrogenation of diolefin hydrocarbons to form olefin hydrocarbons in the presence of a palladium base catalyst, the improvement which comprises adding an aqueous solution of a zinc salt to the diolefin hydro-carbon which is to be hydrogenated, said solution having a weight ratio water/zinc salt of at least 1/1.
2. Process according to claim 1, wherein the amount of zinc salt ranges from 0.01% to 5% by weight with respect to the diolefin compound.
3. Process according to claims 1 or 2, wherein the reaction is carried out at temperatures ranging from 20 to 60°C
and at pressures between 1 and 50 absolute atmospheres.
and at pressures between 1 and 50 absolute atmospheres.
4. Process according to claims 1 or 2, wherein the reaction is carried out in the presence of an amino compound.
5. Process according to claims 1 or 2, wherein the reaction is carried out in the presence of ammonia in amounts not higher than 0.5% by weight of the diolefin compound.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT27492/72A IT963424B (en) | 1972-07-27 | 1972-07-27 | HYDROGENATION PROCESS OF DIOLEFIN HYDRO CARBONS TO OLEFINIC HYDROCARBONS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1046535A true CA1046535A (en) | 1979-01-16 |
Family
ID=11221753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA177,367A Expired CA1046535A (en) | 1972-07-27 | 1973-07-26 | Process for the hydrogenation of diolefin hydrocarbons to olefin hydrocarbons |
Country Status (30)
| Country | Link |
|---|---|
| US (1) | US3857894A (en) |
| JP (1) | JPS5313602B2 (en) |
| AR (1) | AR227263A1 (en) |
| AT (1) | AT328417B (en) |
| AU (1) | AU477097B2 (en) |
| BE (1) | BE802721A (en) |
| BG (1) | BG21008A3 (en) |
| BR (1) | BR7305591D0 (en) |
| CA (1) | CA1046535A (en) |
| CH (1) | CH588428A5 (en) |
| CS (1) | CS176241B2 (en) |
| DD (1) | DD104500A5 (en) |
| DK (1) | DK136524B (en) |
| ES (1) | ES417524A1 (en) |
| FR (1) | FR2194672B1 (en) |
| GB (1) | GB1428287A (en) |
| HU (1) | HU172415B (en) |
| IE (1) | IE38478B1 (en) |
| IN (1) | IN139205B (en) |
| IT (1) | IT963424B (en) |
| LU (1) | LU68103A1 (en) |
| NL (1) | NL169724C (en) |
| NO (1) | NO139858C (en) |
| PL (1) | PL90383B1 (en) |
| RO (1) | RO70140A (en) |
| SE (1) | SE379533B (en) |
| TR (1) | TR17413A (en) |
| YU (1) | YU35092B (en) |
| ZA (1) | ZA734155B (en) |
| ZM (1) | ZM10573A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3947510A (en) * | 1972-07-27 | 1976-03-30 | Snamprogetti S.P.A. | Hydrogenation of linear hydrocarbon diolefins to linear hydrocarbon olefins |
| US4167529A (en) * | 1977-11-11 | 1979-09-11 | The Goodyear Tire & Rubber Company | Selective hydrogenation of cyclopentadiene to form cyclopentene using Raney nickel catalyst and ammonium hydroxide in the reaction mixture |
| FI66019C (en) * | 1977-12-19 | 1984-08-10 | Unilever Nv | FOERFARANDE FOER SELEKTIV HYDRERING AV TRIGLYCERIDOLJA |
| US4570025A (en) * | 1985-06-14 | 1986-02-11 | Phillips Petroleum Company | Preparation of alkenes and cycloalkenes |
| DE3736557A1 (en) * | 1987-10-28 | 1989-05-11 | Sued Chemie Ag | CATALYST FOR THE SELECTIVE HYDROGENATION OF MULTIPLE UNSATURATED HYDROCARBONS |
| US6620982B1 (en) | 1998-10-07 | 2003-09-16 | Equistar Chemicals, Lp | Method of producing purified cyclopentane |
| CN106694010B (en) * | 2016-12-27 | 2018-08-28 | 重庆建峰工业集团有限公司 | A kind of catalyst and preparation method thereof for half Hydrogenation enol of alkynol |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2456633A (en) * | 1946-11-29 | 1948-12-21 | Universal Oil Prod Co | Catalyst preparation |
| US2728713A (en) * | 1952-09-25 | 1955-12-27 | Exxon Research Engineering Co | High activity reforming catalysts for use in the hydroforming of naphtha |
| FR1323307A (en) * | 1962-05-21 | 1963-04-05 | Basf Ag | Partial hydrogenation of cycloaliphatic compounds containing at least two olefinic double bonds |
| GB1086639A (en) * | 1963-10-29 | 1967-10-11 | Geigy Uk Ltd | Production of cyclododecene |
| CH462809A (en) * | 1964-06-03 | 1968-09-30 | Hoffmann La Roche | Use of organosulfur compounds to increase the selectivity of hydrogenation catalysts |
| US3408415A (en) * | 1965-09-20 | 1968-10-29 | Uniroyal Inc | Catalytic hydrogenation |
| US3418386A (en) * | 1966-07-05 | 1968-12-24 | Columbian Carbon | Hydrogenation of cyclooctadienes to cyclooctenes |
| US3433842A (en) * | 1967-04-12 | 1969-03-18 | Universal Oil Prod Co | Process for the hydrogenation of trans,cis-1,5-cyclodecadiene to ciscyclodecene |
| US3433843A (en) * | 1967-10-09 | 1969-03-18 | Universal Oil Prod Co | Selective hydrogenation of trans,cis-1,5-cyclodecadiene to cis-cyclodecene |
| DE2025411A1 (en) * | 1970-05-25 | 1971-12-09 |
-
1972
- 1972-07-27 IT IT27492/72A patent/IT963424B/en active
-
1973
- 1973-06-20 ZA ZA734155A patent/ZA734155B/en unknown
- 1973-06-26 ZM ZM105/73*UA patent/ZM10573A1/en unknown
- 1973-06-26 YU YU1719/73A patent/YU35092B/en unknown
- 1973-06-26 CS CS4591A patent/CS176241B2/cs unknown
- 1973-06-27 RO RO7375259A patent/RO70140A/en unknown
- 1973-06-28 AU AU57469/73A patent/AU477097B2/en not_active Expired
- 1973-07-05 TR TR17413A patent/TR17413A/en unknown
- 1973-07-05 JP JP7533473A patent/JPS5313602B2/ja not_active Expired
- 1973-07-16 IE IE1194/73A patent/IE38478B1/en unknown
- 1973-07-17 GB GB3408373A patent/GB1428287A/en not_active Expired
- 1973-07-17 BG BG24125A patent/BG21008A3/xx unknown
- 1973-07-18 CH CH1052073A patent/CH588428A5/xx not_active IP Right Cessation
- 1973-07-18 IN IN1682/CAL/73A patent/IN139205B/en unknown
- 1973-07-20 FR FR7326822A patent/FR2194672B1/fr not_active Expired
- 1973-07-24 ES ES417524A patent/ES417524A1/en not_active Expired
- 1973-07-24 BE BE133808A patent/BE802721A/en unknown
- 1973-07-24 US US00382055A patent/US3857894A/en not_active Expired - Lifetime
- 1973-07-25 DD DD172509A patent/DD104500A5/xx unknown
- 1973-07-25 BR BR5591/73A patent/BR7305591D0/en unknown
- 1973-07-26 NL NLAANVRAGE7310423,A patent/NL169724C/en not_active IP Right Cessation
- 1973-07-26 PL PL1973164309A patent/PL90383B1/pl unknown
- 1973-07-26 DK DK414073AA patent/DK136524B/en not_active IP Right Cessation
- 1973-07-26 NO NO3023/73A patent/NO139858C/en unknown
- 1973-07-26 SE SE7310415A patent/SE379533B/xx unknown
- 1973-07-26 CA CA177,367A patent/CA1046535A/en not_active Expired
- 1973-07-26 AT AT658773A patent/AT328417B/en not_active IP Right Cessation
- 1973-07-26 LU LU68103A patent/LU68103A1/xx unknown
- 1973-07-26 HU HU73SA00002513A patent/HU172415B/en unknown
- 1973-10-17 AR AR249129A patent/AR227263A1/en active
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