CA1075721A - Process for the addition of alcohols to acetylenic compounds contained in organic or inorganic hydrocarbon streams - Google Patents
Process for the addition of alcohols to acetylenic compounds contained in organic or inorganic hydrocarbon streamsInfo
- Publication number
- CA1075721A CA1075721A CA256,494A CA256494A CA1075721A CA 1075721 A CA1075721 A CA 1075721A CA 256494 A CA256494 A CA 256494A CA 1075721 A CA1075721 A CA 1075721A
- Authority
- CA
- Canada
- Prior art keywords
- alkali
- hydrocarbon stream
- mixtures
- ions
- gem
- 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
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/14875—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds
- C07C7/14891—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound with organic compounds alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
- C07C41/08—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only to carbon-to-carbon triple bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (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 invention relates to a process for the removal of acetylenic compounds from a hydrocarbon stream which comprises the steps of: (a) reacting an alcohol or glycol with the acetylenic compounds in the hydrocarbon stream to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place in the presence of an acid ion exchange resin catalyst wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof. The acetylenic compounds obtained thereby constitute industrially interesting compounds.
The invention relates to a process for the removal of acetylenic compounds from a hydrocarbon stream which comprises the steps of: (a) reacting an alcohol or glycol with the acetylenic compounds in the hydrocarbon stream to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place in the presence of an acid ion exchange resin catalyst wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof. The acetylenic compounds obtained thereby constitute industrially interesting compounds.
Description
1-)75'7;~1 The present invention relates to a process for the removal of acetylenic compounds from a hydrocarbon stream.
More particularly, the present invention relates to a process which permits both organic or inorganic, hydrocarbon streams to be purified, and the same acetylenic compounds to be used for the simultaneous production of industrially inte-resting products.
Even more particularly the present invention relates to a method:
1. For the removal from a hydrocarbon stream comprising ethylene, propylene and butylene, either alone or in admixture with other saturated or unsaturated hydrocarbons having the same number of carbon atoms t of acetylene, propyne, l-butyne, 2-butyne, vinylacety-lene an~ dia~etylene, with simultaneous production of vi-nyl ethers and/or of the gem-diethers ofthesa~e compounds
More particularly, the present invention relates to a process which permits both organic or inorganic, hydrocarbon streams to be purified, and the same acetylenic compounds to be used for the simultaneous production of industrially inte-resting products.
Even more particularly the present invention relates to a method:
1. For the removal from a hydrocarbon stream comprising ethylene, propylene and butylene, either alone or in admixture with other saturated or unsaturated hydrocarbons having the same number of carbon atoms t of acetylene, propyne, l-butyne, 2-butyne, vinylacety-lene an~ dia~etylene, with simultaneous production of vi-nyl ethers and/or of the gem-diethers ofthesa~e compounds
2. For the removal from butadiene streams (either alone or in admixture with saturated or unsaturated hydro-carbons having the same number of carbon atoms, of propyn~, l-butyne, 2-butyne, vinylacetylene and/or diacetylene, with the simultaneous production of the vinyl ethers andjor of the gem-diethers of the same compounds.
3. For the removal from propylene streams (either alone or in admixture with other saturated or unsaturated hydrocarbons having the same number of carbon atoms), of the propyne, with the simultaneous production of corresponding vinyl ether and/or gem-diether.
4. For the removal from ethylene streams (either alone or in admixture with ethane) or the acetylene with the simultaneous production of corresponding vinyl ether and/or gem-diether.
~,,~ ~
10'~5~1 It is known that in most uses the olefinic, saturated hydrocarbons, and particularly the dienic hydrocarbons must be free from acetylenic compounds; for instance their content in the butadiene monomer must be ~ 50 ppm, owing to their poisoning action on the polymerization catalysts.
A number of methods have been proposed and are actually used for the removal of the acetylenic compounds; these methods permit the desired content to be obtained, but require essentially high operating costs and/or particular equipments and thus high investment costs.
It has been found that the acetylenic compounds can be totally removed without having recourse to the operations of the prior art, considerable economic advantages being simultaneously obtained both due to the simplicity of the operations proposed in substitution for those actually used, and for the simultaneous use of the acetylenic compounds (the streams rich in these compounds being normally disposed by flame burning), through their conversion into industrially interesting compounds.
The object of the present invention is a process for the removal of acetylenic compounds from a hydrocarbon stream which comprises the steps of :
(a) reacting an alcohol or glycol with the acetylenic compounds in the hydrocarbon stream to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place in the presence of an acid ion exchange resin catalyst wherein the acid groups havè been totally replaced by mercuric ions (Hg~+ ions) and ions of alkali-earth metals (Me n~ ions); and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers,`
or mixtures thereof.
~ ~ 2 -,~
.
1~757'Zl The ion exchange resin which is used has, as above indicated, acid property and preferably contains sulphonic groups ~ .
~0'757;~1 (-SO3H groups supported onto resins, for example polystyrene, divinylbenzene or polyphenolic resins), but resins containing -COOH groups, preferably supported onto acrylic resins,can also be used.
Generally, the ions of the afore-mentioned metals can be added to the resin in form of their salts, e.g. as mercuric and sodium nitrate or acetate, but to this end hydroxides can also be used (for instance sodium can be added in the hydroxide form); the content of Hg+~ ions of the resin can also be higher than that of the Men+ ions.
It is preferred that firstly the Men~ ions and then the Hg~+ ions are added to the resins; it is also preferable that during the operation aqueous solutions are employed and that the resin, after the treatment, is dehydrated by washing with metha-nol or, generally, with the alcohol used in the reaction.
The hydrocarbon streams which can be processed according to the present invention are paraffinic, olefinic and dienic streams (par~icularly streams rich in ethylene, propylene, butadiene, acetylene, propyne, l-butyne, 2-butyne, vinylacetylene, 2Q and diacetylene). The hydrocarbon stream also comprises satura-ted or unsaturated hydrocarbons having from 2 to 4 carbon atoms.
The addition can be carried out within a wide range of temperatures and pressures; the treatment is advantageously carried out between -20C and ~80C, and more suitably between 10C and 50C, under a pressure selected so as to maintain, at - the operating temperature, the hydrocarbon streams under treat-ment either in liquid ox in gaseous phase (depending on the opportunity of treating these streams in vapour or liquid phase).
By operating in liquid phase, the spatial velocity (LHSV) of the reaction is of between 0.1 and 100 (cu.cm/h.g). It is advisable to carry out the treatment in the presence of a stoichiometric excess of the alcohol or glycol with respect to the acetylenic compounds: as a matter of fact a molar ratio (alcohol/total acetylenic compounds) = 1.05 - 2.1 is suitably adopted, particu-.
1(1757;~
larly depending on whether vinyl ethers or gcm-diethers are desired.
It is o interest to point out that, by operating accor-ding to the present invention, the resins totally exchanged with mercuric ions as well as with ions of alkali and earth-alkali metals maintain their activity for a period at least three times higher than the resins without ions of alkali or earth-alkali metals. This is probably also due to the fact that in the case of the resins treated according to the in-vention~ the secondary reactions normally occurring in the presence of acid ion exchange resins are of minor importance.
Some examples having the purpose of better illustrating the invention, without anyhow limiting it, shall be now provided.
EXAMPLE
98 g of acid resin of the Amberlyst 15 type (containing acid groups such as those of the -S03H type) are treated with 2 lt of a 10% by weight aqueous solution of NaOH; the mixture is stirred for one hour and then filtered~ and the resin is washed with distilled water until a neutral reaction is obtain-ed. The same resin is thereafter treated with 300 mls of an aqueous solution~ made acid by acetic acid~ containing 2 g.ions of Hg~ (as mercuric acetate); the mixture is kept under stirr~ng for 24 hours and then filtered under vacuum and repeatedly washed with anhydrous methanol.
- A part of the thus treated resin is charged in a 10 ml volume reactor, maintained at 40C by means of a thermostatic circuit. Under a pressure of 10 relative atmospheres~ 50 mls of a C4 stream, rich in butadiene (about 55% ~, and containing about ~300 ppm of vinylacetylene, about 1500 ppm of l-butyne~
and about 1000 ppm of propyne~ are continuously fed by a pump together with methanol in an amount such as the alcohol/total 10757;~1 acetylenic compounds is 2.1 moles/mole.
The content of all the three aforesaid acetylenic compounds as determined in the samples of tne liquid effluent from the reactor (the samples being taken every 5 hours) is always ~ 10 ppm throughout the time of the test (120 hours ).
In the same reactor of the Example l~ by operating at a temperature of 80C and under a pressure of a40ut 20 relative atmospheres~ 50 mls/h of propylene~ containing 0.3% propy.ne are fed by the pump together with methanol in an amount such as the alcohol/acetylenic compound is 2.1 moles/mole The contents of prop~ne and 2~2-dimethoxypropane~ as determined in the samples of the liquid taken (every 5 hours~ from the reactor effluent throughout the time of the test (300 hours ) are ~ lOppm and o.78% by weight re6pectively.
R
.
~,,~ ~
10'~5~1 It is known that in most uses the olefinic, saturated hydrocarbons, and particularly the dienic hydrocarbons must be free from acetylenic compounds; for instance their content in the butadiene monomer must be ~ 50 ppm, owing to their poisoning action on the polymerization catalysts.
A number of methods have been proposed and are actually used for the removal of the acetylenic compounds; these methods permit the desired content to be obtained, but require essentially high operating costs and/or particular equipments and thus high investment costs.
It has been found that the acetylenic compounds can be totally removed without having recourse to the operations of the prior art, considerable economic advantages being simultaneously obtained both due to the simplicity of the operations proposed in substitution for those actually used, and for the simultaneous use of the acetylenic compounds (the streams rich in these compounds being normally disposed by flame burning), through their conversion into industrially interesting compounds.
The object of the present invention is a process for the removal of acetylenic compounds from a hydrocarbon stream which comprises the steps of :
(a) reacting an alcohol or glycol with the acetylenic compounds in the hydrocarbon stream to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place in the presence of an acid ion exchange resin catalyst wherein the acid groups havè been totally replaced by mercuric ions (Hg~+ ions) and ions of alkali-earth metals (Me n~ ions); and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers,`
or mixtures thereof.
~ ~ 2 -,~
.
1~757'Zl The ion exchange resin which is used has, as above indicated, acid property and preferably contains sulphonic groups ~ .
~0'757;~1 (-SO3H groups supported onto resins, for example polystyrene, divinylbenzene or polyphenolic resins), but resins containing -COOH groups, preferably supported onto acrylic resins,can also be used.
Generally, the ions of the afore-mentioned metals can be added to the resin in form of their salts, e.g. as mercuric and sodium nitrate or acetate, but to this end hydroxides can also be used (for instance sodium can be added in the hydroxide form); the content of Hg+~ ions of the resin can also be higher than that of the Men+ ions.
It is preferred that firstly the Men~ ions and then the Hg~+ ions are added to the resins; it is also preferable that during the operation aqueous solutions are employed and that the resin, after the treatment, is dehydrated by washing with metha-nol or, generally, with the alcohol used in the reaction.
The hydrocarbon streams which can be processed according to the present invention are paraffinic, olefinic and dienic streams (par~icularly streams rich in ethylene, propylene, butadiene, acetylene, propyne, l-butyne, 2-butyne, vinylacetylene, 2Q and diacetylene). The hydrocarbon stream also comprises satura-ted or unsaturated hydrocarbons having from 2 to 4 carbon atoms.
The addition can be carried out within a wide range of temperatures and pressures; the treatment is advantageously carried out between -20C and ~80C, and more suitably between 10C and 50C, under a pressure selected so as to maintain, at - the operating temperature, the hydrocarbon streams under treat-ment either in liquid ox in gaseous phase (depending on the opportunity of treating these streams in vapour or liquid phase).
By operating in liquid phase, the spatial velocity (LHSV) of the reaction is of between 0.1 and 100 (cu.cm/h.g). It is advisable to carry out the treatment in the presence of a stoichiometric excess of the alcohol or glycol with respect to the acetylenic compounds: as a matter of fact a molar ratio (alcohol/total acetylenic compounds) = 1.05 - 2.1 is suitably adopted, particu-.
1(1757;~
larly depending on whether vinyl ethers or gcm-diethers are desired.
It is o interest to point out that, by operating accor-ding to the present invention, the resins totally exchanged with mercuric ions as well as with ions of alkali and earth-alkali metals maintain their activity for a period at least three times higher than the resins without ions of alkali or earth-alkali metals. This is probably also due to the fact that in the case of the resins treated according to the in-vention~ the secondary reactions normally occurring in the presence of acid ion exchange resins are of minor importance.
Some examples having the purpose of better illustrating the invention, without anyhow limiting it, shall be now provided.
EXAMPLE
98 g of acid resin of the Amberlyst 15 type (containing acid groups such as those of the -S03H type) are treated with 2 lt of a 10% by weight aqueous solution of NaOH; the mixture is stirred for one hour and then filtered~ and the resin is washed with distilled water until a neutral reaction is obtain-ed. The same resin is thereafter treated with 300 mls of an aqueous solution~ made acid by acetic acid~ containing 2 g.ions of Hg~ (as mercuric acetate); the mixture is kept under stirr~ng for 24 hours and then filtered under vacuum and repeatedly washed with anhydrous methanol.
- A part of the thus treated resin is charged in a 10 ml volume reactor, maintained at 40C by means of a thermostatic circuit. Under a pressure of 10 relative atmospheres~ 50 mls of a C4 stream, rich in butadiene (about 55% ~, and containing about ~300 ppm of vinylacetylene, about 1500 ppm of l-butyne~
and about 1000 ppm of propyne~ are continuously fed by a pump together with methanol in an amount such as the alcohol/total 10757;~1 acetylenic compounds is 2.1 moles/mole.
The content of all the three aforesaid acetylenic compounds as determined in the samples of tne liquid effluent from the reactor (the samples being taken every 5 hours) is always ~ 10 ppm throughout the time of the test (120 hours ).
In the same reactor of the Example l~ by operating at a temperature of 80C and under a pressure of a40ut 20 relative atmospheres~ 50 mls/h of propylene~ containing 0.3% propy.ne are fed by the pump together with methanol in an amount such as the alcohol/acetylenic compound is 2.1 moles/mole The contents of prop~ne and 2~2-dimethoxypropane~ as determined in the samples of the liquid taken (every 5 hours~ from the reactor effluent throughout the time of the test (300 hours ) are ~ lOppm and o.78% by weight re6pectively.
R
.
Claims (15)
1. A process for the removal of acetylenic compounds from a hydrocarbon stream which comprises the steps of:
(a) reacting an alcohol or glycol with the acetylenic compounds in the hydrocarbon stream to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place in the presence of an acid ion exchange resin catalyst wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
(a) reacting an alcohol or glycol with the acetylenic compounds in the hydrocarbon stream to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place in the presence of an acid ion exchange resin catalyst wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
2. A process for the removal of acetylene, propyne, l-butyne, 2-butyne, vinylacetylene, diacetylene, or mixtures thereof from a hydrocarbon stream which comprises the steps of:
(a) reacting methanol or ethylene glycol with acetylene, propyne, l-butyne, 2-butyne, vinylacetylene, diacety-lene, or mixtures thereof to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place at a temperature in the range of -20°C to 80°C in the presence of an acid ion exchange catalyst wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
(a) reacting methanol or ethylene glycol with acetylene, propyne, l-butyne, 2-butyne, vinylacetylene, diacety-lene, or mixtures thereof to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place at a temperature in the range of -20°C to 80°C in the presence of an acid ion exchange catalyst wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
3. The process as claimed in claim 2, wherein the acid ion exchange resin contains sulphonic groups.
4. The process as claimed in claim 3, wherein the sulphonic acid groups are supported on polystyrene, divinyl-benzene, or polyphenolic resins, or mixtures thereof.
5. The process as claimed in claim 2, wherein the acid ion exchange resin contains carboxylic groups.
6. The process as claimed in claim 5, wherein the carboxylic groups are supported on acrylic resins.
7. The process as claimed in claim 2, wherein the mercury ions are added to the resin in the form of a mercury salt.
8. The process as claimed in claim 7, wherein the mercury salt is mercury nitrate or mercury acetate.
9. The process as claimed in claim 2, wherein the alkali or alkali-earth metal ions are added to the resin in the form of salts or hydroxides.
10. The process as claimed in claim 9, wherein the alkali or alkali-earth metal ions are added in the form of sodium nitrate, sodium acetate, or sodium hydroxide.
11. The process as claimed in claim 2, wherein the reacting takes place at a temperature in the range of from 10°C to 50°C.
12. The process as claimed in claim 2, wherein the hydrocarbon stream comprises ethylene, propylene, butadiene, acetylene, propyne, l-butyne, 2-butyne, vinylacetylene, and diacetylene.
13. The process as claimed in claim 12, wherein the hydrocarbon stream also comprises saturated or unsaturated hydrocarbons having from 2 to 4 carbon atoms.
14. A process for removing propyne from a hydrocarbon stream consisting of propylene or propylene in admixture with other saturated or unsaturated hydrocarbons having three carbon atoms, which comprises the steps of:
(a) reacting methanol or ethylene glycol with the propyne to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place at a temperature in the range of -20°C to 80°C and in the presence of an acid ion exchange resin wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
(a) reacting methanol or ethylene glycol with the propyne to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place at a temperature in the range of -20°C to 80°C and in the presence of an acid ion exchange resin wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
15. A process for removing acetylene from a hydrocarbon stream consisting of ethene or ethene and ethane, which comprises the steps of:
(a) reacting methanol or ethylene glycol with the acetylene to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place at a temperature in the range of -20°C to 80°C and in the presence of an acid ion exchange resin wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
(a) reacting methanol or ethylene glycol with the acetylene to produce vinyl ethers, gem-diethers, or mixtures thereof, the reaction taking place at a temperature in the range of -20°C to 80°C and in the presence of an acid ion exchange resin wherein the acid groups have been totally replaced by mercuric ions and ions of alkali or alkali-earth metals; and (b) subjecting the reacted hydrocarbon stream from step (a) to distillation to remove the vinyl ethers, gem-diethers, or mixtures thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT25170/75A IT1039739B (en) | 1975-07-08 | 1975-07-08 | PROCEDURE FOR THE ADDITION OF ALCOHOLS TO ACETYLENE COMPOUNDS CONTAINED IN ORGANIC OR INORGANIC HYDROCARBON CURRENTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1075721A true CA1075721A (en) | 1980-04-15 |
Family
ID=11215900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA256,494A Expired CA1075721A (en) | 1975-07-08 | 1976-07-07 | Process for the addition of alcohols to acetylenic compounds contained in organic or inorganic hydrocarbon streams |
Country Status (34)
| Country | Link |
|---|---|
| JP (1) | JPS602286B2 (en) |
| AR (1) | AR217057A1 (en) |
| AT (1) | AT345262B (en) |
| AU (1) | AU501768B2 (en) |
| BE (1) | BE843916A (en) |
| BR (1) | BR7605718A (en) |
| CA (1) | CA1075721A (en) |
| CH (1) | CH626266A5 (en) |
| CS (1) | CS194769B2 (en) |
| DD (2) | DD131012A5 (en) |
| DE (1) | DE2630769C3 (en) |
| DK (1) | DK303676A (en) |
| EG (1) | EG12170A (en) |
| ES (1) | ES449923A1 (en) |
| FR (1) | FR2317265A1 (en) |
| GB (1) | GB1519714A (en) |
| HU (1) | HU178721B (en) |
| IE (1) | IE43609B1 (en) |
| IN (1) | IN145252B (en) |
| IT (1) | IT1039739B (en) |
| LU (1) | LU75304A1 (en) |
| MX (1) | MX142865A (en) |
| NL (1) | NL7607524A (en) |
| NO (1) | NO762204L (en) |
| PH (1) | PH15669A (en) |
| PL (1) | PL108186B1 (en) |
| PT (1) | PT65330B (en) |
| RO (1) | RO70953A (en) |
| SE (1) | SE7607852L (en) |
| SU (1) | SU991943A3 (en) |
| TR (1) | TR18958A (en) |
| YU (1) | YU37303B (en) |
| ZA (1) | ZA763797B (en) |
| ZM (2) | ZM8876A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3700605A1 (en) * | 1987-01-10 | 1988-07-21 | Huels Chemische Werke Ag | METHOD FOR PRODUCING ALKOXIBUTENINES |
| GB9314514D0 (en) * | 1993-07-13 | 1993-08-25 | Ici Plc | Hydrocarbon processing |
| KR102561860B1 (en) * | 2016-10-25 | 2023-08-02 | 삼성전자주식회사 | Electronic apparatus and control method thereof |
-
1975
- 1975-07-08 IT IT25170/75A patent/IT1039739B/en active
-
1976
- 1976-06-25 NO NO762204A patent/NO762204L/no unknown
- 1976-06-25 ZA ZA763797A patent/ZA763797B/en unknown
- 1976-06-30 AU AU15433/76A patent/AU501768B2/en not_active Expired
- 1976-06-30 YU YU1611/76A patent/YU37303B/en unknown
- 1976-07-01 ZM ZM88/76A patent/ZM8876A1/en unknown
- 1976-07-01 ZM ZM89/76A patent/ZM8976A1/en unknown
- 1976-07-05 DK DK303676A patent/DK303676A/en not_active Application Discontinuation
- 1976-07-06 LU LU75304A patent/LU75304A1/xx unknown
- 1976-07-06 DD DD7600200187A patent/DD131012A5/en unknown
- 1976-07-06 ES ES449923A patent/ES449923A1/en not_active Expired
- 1976-07-06 GB GB28109/76A patent/GB1519714A/en not_active Expired
- 1976-07-06 EG EG406/76A patent/EG12170A/en active
- 1976-07-06 TR TR18958A patent/TR18958A/en unknown
- 1976-07-06 IN IN1195/CAL/1976A patent/IN145252B/en unknown
- 1976-07-06 CS CS764465A patent/CS194769B2/en unknown
- 1976-07-06 DD DD193731A patent/DD127082A5/xx unknown
- 1976-07-07 HU HU76SA2942A patent/HU178721B/en unknown
- 1976-07-07 IE IE1501/76A patent/IE43609B1/en unknown
- 1976-07-07 CA CA256,494A patent/CA1075721A/en not_active Expired
- 1976-07-07 RO RO7686863A patent/RO70953A/en unknown
- 1976-07-07 FR FR7620819A patent/FR2317265A1/en active Granted
- 1976-07-07 NL NL7607524A patent/NL7607524A/en not_active Application Discontinuation
- 1976-07-07 AT AT498676A patent/AT345262B/en not_active IP Right Cessation
- 1976-07-07 CH CH872876A patent/CH626266A5/en not_active IP Right Cessation
- 1976-07-07 PT PT65330A patent/PT65330B/en unknown
- 1976-07-08 BR BR7605718A patent/BR7605718A/en unknown
- 1976-07-08 MX MX165436A patent/MX142865A/en unknown
- 1976-07-08 AR AR263906A patent/AR217057A1/en active
- 1976-07-08 PH PH18662A patent/PH15669A/en unknown
- 1976-07-08 SE SE7607852A patent/SE7607852L/en not_active Application Discontinuation
- 1976-07-08 JP JP51080430A patent/JPS602286B2/en not_active Expired
- 1976-07-08 BE BE168743A patent/BE843916A/en not_active IP Right Cessation
- 1976-07-08 PL PL1976191024A patent/PL108186B1/en unknown
- 1976-07-08 DE DE2630769A patent/DE2630769C3/en not_active Expired
- 1976-07-08 SU SU762379661A patent/SU991943A3/en active
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