GB2072668A - Process for reducing the water content of alcohol-water mixtures - Google Patents
Process for reducing the water content of alcohol-water mixtures Download PDFInfo
- Publication number
- GB2072668A GB2072668A GB8108640A GB8108640A GB2072668A GB 2072668 A GB2072668 A GB 2072668A GB 8108640 A GB8108640 A GB 8108640A GB 8108640 A GB8108640 A GB 8108640A GB 2072668 A GB2072668 A GB 2072668A
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- mixture
- water
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- ethanol
- alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
- C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
- C12C11/00—Fermentation processes for beer
- C12C11/02—Pitching yeast
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Mycology (AREA)
- General Chemical & Material Sciences (AREA)
- Food Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
An improved process is disclosed for producing petrol-grade C2-C4 alcohols from aqueous mixtures which contain these alcohols. The improvement is that the aqueous mixture is reacted with a tertiary olefin in the presence of a catalyst having an acidic character, preferably at a temperature of from 40 to 90 DEG C and at a space velocity of from 5 to 25 litres of reactants per litre of catalyst per hour. Preferred catalysts are acidic ion-exchange resins, especially those having -SO3H groups. The temperature and space velocity ranges are critical in order to minimize the parasitic ether- forming reaction.
Description
SPECIFICATION
Process for reducing the water content of alcohol-water mixtures
This invention relates to a process for reducing the water content of alcohol-water mixtures, for example a process for producing petrol-grade C2-C4 alcohols from aqueous mixtures containing them.
It is known that ethanol have very appreciable octane-number characteristics so that it can be used as such in the formulation of fuel mixtures to reduce the percentage of lead-alkyl additives or to reduce the aromatics content of petrol.
Ethanol is conventionally produced on a commerical scale by the fermentation of carbohydrates. In these procedures, the percentage of alcohol in the fermentation products of sugar-containing juices is below 10%.
The subsequent steps directed to recovering alcohol comprise a sequence of distillation steps by which there is obtained a water-ethanol azeotropic mixture which, under atmospheric pressure, has a water content of 4.4% by weight. However, this ethanol still contains too much water for it to be employed directly in fuels, so that further dehydration stages are necessary.
The rectification stages and, more particularly, the final dehydration stage, increase the cost of petrol-grade ethanol. This has been conducive to a number of studies dealing with the optimization of heat recovery in conventional systems and also to a number of suggestions for alternative dehydration procedures. Absolute ethanol is obtained at present by azeotropic distillation with benzene. Alternative suggestions have been made recently however, these being based on the stripping of water by the selective absorption on starchy substances, by the preferential absorption on textile fibres, by extraction with solvents in critical phase, by the use of membranes which are impervious to either component, by the absorption on molecular sieves having pore dimensions sufficient to retain water, and by distillation procedures under reduced pressure.All the suggested approaches, however, have the serious drawbacks that they involve a decrease of the liquid product yield and require special apparatus so that the costs are high.
According to the present invention, there is provided a process for reducing the water content of an alcohol-water mixture, which comprises treating the mixture with at least one tertiary olefin or with an olefin mixture containing at least one tertiary olefin in the presence of an acidic catalyst.
An embodiment of the present invention provides a process for the preparation of petrol-grade C2-C4 alochols, comprising the step of reacting an alcohol-water mixture from a relevant production process with either a tertiary olefin or an olefin cut containing it. By so doing, the water content is reduced since water, by reacting with the olefin concerned, produces a tertiary alcohol. The resultant product, upon stripping the unreated olefins, is a mixture which can be added to fuels in the usual amounts without the occurrence of phase separation, even at temperatures below -20 C.
The addition reaction of the tertiary olefin to water can be carried out with the aid of conventional catalysts as used for olefin hydrations, such as mineral acids, Lewis acids and ion-exchange resins. In particular, ion-exchange resins supporting -S03H groups on polystyrene, divinylbenzene and polyphenol matrices are preferred due to their greater simplicity of use.
The working conditions should be carefully selected, inasmuch as too high temperatures or too low spatial velocities worsen the selectivity of the process because the competing reaction, namely the formation of the corresponding ethers, might predominate. The latter reaction should be prevented as far as practicable because it reduces the amount of tertiary olefin reacting with the water, the result being that the production of the tertiary alcohol is decreased. The tertiary alcohol is important since it has a solubilizing action on the water residue.
It is preferred that the addition reaction be carried out at a temperature of from 40 to 90"C under a pressure which is so selected as to maintain the hydrocarbon stream being processed either in the liquid or the gaseous phase, depending upon whether it is desired to process the stream concerned in the vapour phase or the liquid phase. When working in the liquid phase, the spatial velocity (LHSV) of the reaction, expressed in litres of feed per litre of catalyst per hour, is preferably from 5 to 25.
For a better understanding of the invention, reference will now be made, by way of example, to the drawing. Figure 1 of the drawing illustrates a particular embodiment of the process according to the present invention, relating to the treatment of an aqueous mixture which contains ethanol with an olefin fraction which contains isobutene. The alcoholic mixture 1 and the olefin fraction 3, together with recycled olefins 2, are fed to a reactor R-l. The reaction product 5 is sent to a rectification column C-l,from the bottom 6 of which ethanol is recovered together with the reaction product and unreacted water. At the column head 7, an olefin fraction is recovered, a portion 2 of this fraction being recycled to the reactor R-1 and a portion 8 of this fraction being removed from the process.Figure 2 shows a process similar to that of Figure 1, without olefin recycling.
The invention will now be illustrated by the following Examples, in which all parts and percentages are by weight.
In Example I there is described a process of the invention. As can be seen from Example 1, it is possible to obtain a product which is perfectly miscible with petrol even at low temperatures, while concurrently achieving an improvement in yield, relative to the starting alcohol, of the order of magnitude of 18% at the expense of a gaseous product, namely isobutene (which has not been directly added to petrol as this is not possible).
A comparison between the results of Example 2 and those of Example 3 shows how important it is to limit the conversion of ethanol. As a matter of fact, by working at a lower space velocity, there is obtained a product which, when mixed with petrol, has a higher turbidity temperature.
A comparison between the results of Examples 4, 5 and 6 shows that, for the same spatial velocity, the reaction temperature is critical, the optimum value being 70 C.
Example 1
In a tubular reaction R-l of Figure 1, which contained a macroporous acid-form ion-exchange resin such as
Amberlyst 15 (Registered Trade Mark), a mixture of 28.20 parts of ethanol 1 (containing 7% of water), 61.50 parts of a recycled olefin fraction 2 containing 6.4% of isobutene and 10.36 parts of an olefin fraction 3 containing 50% of isobutene was reacted. The composition of the mixture 4 was as follows:
Non-reactive butenes . . 62.7% Isobutene . . . 9.1 % Ethanol . . 26.2%
Water . . 2.0%.
The mixture 4, fed into the reactor at a space velocity of 10 litres per hour per litre of catalyst, was reacted at a temperature of 70 C, and the following reaction product 5 was obtained:
Unreacted butenes .. . 62.7% Isobutene . .. 4.3%
Ethyl tert-butyl ether . . 3.6%
Tert-butyl alcohol . . 3.8%
Ethanol . . 24.6% Water . . 1.0%.
Subsequent fractionation of the reaction product was carried out in the rectification column C1 to obtain 33.0 parts of a bottom product 6 having the following composition:
Ethanol . . 74.5%
Water . . 3.0% Tert-butyl alcohol . . 11.5%
Ethyl Tert-butyl ether . 11.0%.
Also obtained were 67 parts of a head product 7 having the following composition:
Unreacted butenes . - 93.6% Isobutene . . 16.4% The head product 7 was separated into two portions 2 and 8, the former (61.5 parts) being recycled and the latter (5.5 parts) being used as a by-product.
The bottom product 6 could be directly mixed with petrol without any demixing problems.
By way of comparison, the values of the turbidity temperature of the ethanol 1 (mixture A) and of the reaction product 6 (mixture B), both mixed in an amount of 10% with a hydrocarbon stream containing 30% of aromatics and 70% of saturated hydrocarbons, were as follows:
Mixture A . . above + 20"C Mixture B . . under -20 C.
Example 2
In the tubular reactor R-l of Figure 2 containing a macroporous acid-form ion-exchange resin such as
Amberlyst 15, a mixture of 34.1 parts of ethanol 1(7.3% water) and 65.9 parts of an olefin fraction 2 containing 50.7% of isobutene was reacted. The composition of the mixture 3 was as follows:
Non-reactive butenes . . 32.5%
Isobutene . 33.4% Ethanol . . 31.6%
Water . 2.5%
The mixture 3, fed into the reactor at a space velocity of 1.5 litres per hour per litre of catalyst, was reacted at a temperature of 60"C to obtain a reaction product 4 having the following composition: Un reacted butenes . .32.5%
Isobutene . . 2.5%
Ethyl tert-butyl ether . . 45.7%
Tert-butyl alcohol . . 7.9%
Ethanol .. 10.7%
Water . . 0.7%
Subsequent fractionation of the reaction product 4 was carried out in the rectification column C-i to obtain 65 parts of a bottom product 5 having the following composition:
Ethyl tert-butyl ether . 70.4%
Tert-butyl alcohol . 12.1%
Ethanol . . 16.4%
Water . 1.1 % The water content of the product 5, based on the sum of the alcohols present, was 3.7%.
The column head product 6 consisted of 35.0 parts of an olefin fraction having the following composition:
Unreacted butenes . 92.9%
Isobutene . . 7.1%
The tubidity temperature of a mixture of 10% of the bottom product 5 and 90% of a hydrocarbon fraction (70% of saturated hydrocarbons and 30% of aromatics) was -12"C.
Example 3
In the tubular reactor R-1 of Figure 2, containing a macroporous acid-form ion-exchange resin such as
Amberlyst 15, a mixture of 34.2 parts of ethanol 1 (7.8% water content) and 65.8 parts of an olefin fraction 2 containing 48.2% of isobutene was reacted. The composition of the mixture 3 was as follows:
Non-reactive butenes . . 34.1%
Isobutene . ........ ......... . 31.7%
Ethanol . ........ . . 31.5%
Water . . 2.7%
The mixture 3, fed into the reactor at a space velocity of 16 litres per litre of catalyst per hour, was reacted at a temperature of 60 C, and the following reaction product 4 was obtained:
Unreacted butenes .. . 34.1%
Isobutene . . 22.9%
Ethyl tert-butyl ether . .. 5.5%
Tert-butyl alcohol . .. 7.9%
Ethanol . . 28.9%
Water .. 0.7%
Subsequent fractionation of the reaction product 4 was carried out in the rectification column C-i to obtain 43.0 parts of bottom product 5 having the following composition:
Ethyl tert-butyl ether . 12.8%
Tert-butyl alcohol . . 18.4%
Ethanol 67.2%
Water . . 1.6%.
The water content of the product 5, based on the sum of the alcohols present, was 1.8%.
The column head product 6 consisted of 57.0 parts of an olefin fraction having the following compositon:
Unreacted butenes .. . 59.8%
Isobutene . . 40.2%
The turbidity temperature of a mixture of 10% of the column bottom product5 with 90% of a hydrocarbon fraction (70% of saturated hydrocarbons and 30% of aromatics) was under -20 C.
Example 4
In the tubular reactor R-l of Figure 2, containing a macroporous acid-form ion-exchange resin such as
Amberlyst 15, a mixture of 31.5 parts of ethanol 1 (7.5% water content) and 68.5 parts of an olefin fraction 2 containing 50.8% of isobutene was reacted. The composition of the mixture 3 was as follows:
Non-reactive butenes . . 33.7%
Isobutene . . 34.8%
Ethanol . . 29.1%
Water . . 2.4%
The mixture 3, fed into the reactor at a space velocity of 20 litres per litre of catalyst per hour, was reacted at a temperature of 60 C, and the following reaction product 4 was obtained: Unreacted butenes .. ........ ....... .... .33.7% Isobutene .. 25.7%
Ethyl tert-butyl ether . ....... ....... .. 6.5%
Tert-butyl alcohol . . 7.2%
Ethanol . . 26.2% Water . . 0.7%.
Subseuqent fractionation of the reaction product 4 was carried out in the rectification column C-1 to obtain 40.6 parts of bottom product 5 having the following composition:
Ethyl tert-butyl ether . . 16.0%
Tert-butyl alcohol 17.7%
Ethanol . 64.6%
Water . 1.7% The water content of the product 4, based on the sum of the alcohols present, was 2.0%.
The column head product 6 consisted of 59.4 parts of an olefin fraction having the following composition:
Unreacted butenes .. . 56.7% Isobutene . . 43.3%.
Example 5
In the tubular reactor R-l of Figure 2, containing a macroporous acid-form ion-exchange resin such as
Amberlyst 15, a mixture of 31.5 parts of ethanol 1 (7.5% water content) and 68.5 parts of an olefin fraction 2 containing 50.8% of isobutene was reacted. The composition of the mixture 3 was as follows:
Non-reactive butenes . . 33.7%
Isobutene . . 34.8%
Ethanol . . 29.1%
Water . 2.4%.
The mixture 3, fed into the reactor at a space velocity of 20 litres per litre of catalyst per hour, was reacted at a temperature of 70 C, whereby the following reaction product 4 was obtained:
Unreacted butenes . 33.7%
Isobutene . . . 14.0%
Ethyl tert-butyl ether . 27.3%
Tert-butyl alcohol . . 8.1%
Ethanol . 16.5%
Water . 0.4%.
Subsequent fractionation of the reaction product was carried out in the rectification column C-i to obtain 52.3 parts of a bottom product 5 having the following composition:
Ethyl tert-butyl ether .... ............................................................ 52.2%
Tert-butyl alcohol ...... ....... ....................... ............ . 15.5%
Ethanol . ................. ...................................................... 31.5%
Water . .......................... ................... ............. 0.8%
The water content of the product 5, based on the sum of the alcohols present, was 1.7%.
The column head product 6 consisted of 47.7 parts of an olefin fraction having the following composition:
Unreacted butenes .. ....... ....... ......................... ............ . 70.6% Isobutene . ........ .................. 29.4%.
Example 6
In the tubular reactor R-l of Figure 2, containing a macroporous ion-exchange resin of acid-form such as
Amberlyst 15, a mixture of 31.5 parts of ethanol 1 (7.5% water content) and 68.5 parts of an olefin fraction 2 containing 50.8% of isobutene was reacted. The composition of the mixture 3 was as follows:
Non-reactive butenes . ............ ............................ .......... 33.7%
Isobutene . .............. .................. . 34.8%
Ethanol ........ ....... . 29.1%
Water . 2.4%.
The mixture 3, fed into the reactor at a space velocity of 20 litres per litre of catalyst per hour, was reacted at a temperature of 80 C, whereby the following reaction product 4 was obtained:
Unreacted butenes .. . 33.7%
Isobutene .. 9.0%
Ethyl tert-butyl ether . . 37.1%
Ethanol . 12.4%
Water . 0.6%
Subsequent fractionation of the reaction product 4 was carried out in the rectification column C-i to obtain 57.3 parts of a bottom product 5 having the following composition:
Ethyl tert-butyl ether . . 64.7%
Tert-butyl alcohol . . 12.6%
Ethanol . . 21.6%
Water . . 1.1 % The water content of the product 5, based on the sum of the alcohols present, was 3.1%.
The column head product 6 consisted of 42.7 parts of the olefin fraction having the following composition:
Unreacted butenes .. . 78.9%
isobutene . ....... . 21.1%.
Claims (12)
1. A process for reducing the water content of an alcohol-water mixture, which comprises treating the mixture with at least one tertiary olefin or with an olefin mixture containing at least one tertiary olefin in the presence of an acidic catalyst.
2. A process according to claim 1, wherein the acidic catalyst is a mineral acid, a Lewis acid or an acidic ion-exchange resin.
3. A process according to claim 2, wherein the acidic catalyst is an ion-exchange resin containing -SO3H groups.
4. A process according to any of claims 1 to 3, wherein the treatment is carried out at a temperature of from 40 to 900C.
5. A process according to any of claims 1 to 4, wherein the treatment is carried out a space velocity, LHSV, of from 5 to 25 litres pre litre of catalyst per hour.
6. A process according to any of claims 1 to 5, wherein the alcohol is ethanol, propanol or butanol.
7. A process according to any of claims 1 to 6, wherein the tertiary olefin is isobutene.
8. A process according to claim 1, substantiaiiy as described with reference to Figure 1 or Figure 2.
9. A process according to claim 1, substantially as described in any of the foregoing Examples.
10. An alcohol-water mixture whose water content has been reduced by a process according to any of claims 1 to 9.
11. A mixture as claimed in claim 10, from which olefin(s) have been removed.
12. Petrol containing, an an additive, a mixture as claimed in claim 11.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT21068/80A IT1140794B (en) | 1980-03-31 | 1980-03-31 | PROCEDURE FOR THE PRODUCTION OF C2-C4 "GASOLINE" ALCOHOLS FROM AQUEOUS MIXTURES CONTAINING THEM |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2072668A true GB2072668A (en) | 1981-10-07 |
| GB2072668B GB2072668B (en) | 1984-03-28 |
Family
ID=11176255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8108640A Expired GB2072668B (en) | 1980-03-31 | 1981-03-19 | Process for redcucing the water content of alcohol-water mixtures |
Country Status (25)
| Country | Link |
|---|---|
| JP (1) | JPS56151790A (en) |
| AU (1) | AU550088B2 (en) |
| BE (1) | BE888150A (en) |
| BR (1) | BR8101872A (en) |
| CA (1) | CA1160252A (en) |
| CH (1) | CH648340A5 (en) |
| CS (1) | CS221292B2 (en) |
| DD (1) | DD157700A5 (en) |
| DE (1) | DE3112277C2 (en) |
| DK (1) | DK137281A (en) |
| ES (1) | ES501396A0 (en) |
| FR (1) | FR2479186A1 (en) |
| GB (1) | GB2072668B (en) |
| HU (1) | HU192065B (en) |
| IE (1) | IE51127B1 (en) |
| IT (1) | IT1140794B (en) |
| LU (1) | LU83265A1 (en) |
| NL (1) | NL8101594A (en) |
| NO (1) | NO811022L (en) |
| NZ (1) | NZ196606A (en) |
| PL (1) | PL230427A1 (en) |
| RO (1) | RO84498B (en) |
| SE (1) | SE8101977L (en) |
| SU (1) | SU1034610A3 (en) |
| YU (1) | YU41038B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0723331B2 (en) * | 1985-03-12 | 1995-03-15 | 旭化成工業株式会社 | Method for producing tertiary butanol |
| US7007764B2 (en) | 2002-12-06 | 2006-03-07 | Manitowoc Crane Companies, Inc. | Carbody to crawler connection |
| JP2007021643A (en) * | 2005-07-15 | 2007-02-01 | Amada Co Ltd | Work attracting device using permanent magnet |
| US10570071B1 (en) | 2018-12-12 | 2020-02-25 | Saudi Arabian Oil Company | Membrane-based process for butanols production from mixed butenes |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL299568A (en) * | 1900-01-01 | |||
| FR1314120A (en) * | 1962-01-08 | 1963-01-04 | Bayer Ag | Process for the preparation of tert-butyl and alkyl ethers |
| DE1249844B (en) * | 1962-03-21 | 1967-09-14 | GuIf Research &. Development Company, Pittsburgh, Pa (V St A) | Process for the production of alcohols by the addition of water to the corresponding olefins in the liquid phase |
| US3822119A (en) * | 1970-11-19 | 1974-07-02 | Goodyear Tire & Rubber | Anti-pollution anti-knock gasoline |
| DE2629769B2 (en) * | 1976-07-02 | 1980-03-13 | Chemische Werke Huels Ag, 4370 Marl | Process for the production of pure methyl tertiary butyl ether |
| US4087471A (en) * | 1977-05-20 | 1978-05-02 | Petro-Tex Chemical Corporation | Fixed bed process for the production of t-butanol |
-
1980
- 1980-03-31 IT IT21068/80A patent/IT1140794B/en active
-
1981
- 1981-03-18 IE IE602/81A patent/IE51127B1/en unknown
- 1981-03-19 GB GB8108640A patent/GB2072668B/en not_active Expired
- 1981-03-24 NZ NZ196606A patent/NZ196606A/en unknown
- 1981-03-26 FR FR8106118A patent/FR2479186A1/en active Granted
- 1981-03-26 BR BR8101872A patent/BR8101872A/en unknown
- 1981-03-26 NO NO811022A patent/NO811022L/en unknown
- 1981-03-26 DK DK137281A patent/DK137281A/en not_active Application Discontinuation
- 1981-03-27 SE SE8101977A patent/SE8101977L/en not_active Application Discontinuation
- 1981-03-27 BE BE0/204278A patent/BE888150A/en not_active IP Right Cessation
- 1981-03-27 DE DE3112277A patent/DE3112277C2/en not_active Expired
- 1981-03-30 CH CH2146/81A patent/CH648340A5/en not_active IP Right Cessation
- 1981-03-30 HU HU81810A patent/HU192065B/en unknown
- 1981-03-30 YU YU828/81A patent/YU41038B/en unknown
- 1981-03-30 LU LU83265A patent/LU83265A1/en unknown
- 1981-03-30 RO RO103858A patent/RO84498B/en unknown
- 1981-03-30 SU SU813266251A patent/SU1034610A3/en active
- 1981-03-30 PL PL23042781A patent/PL230427A1/xx unknown
- 1981-03-30 JP JP4566881A patent/JPS56151790A/en active Pending
- 1981-03-30 AU AU68903/81A patent/AU550088B2/en not_active Ceased
- 1981-03-30 CA CA000374128A patent/CA1160252A/en not_active Expired
- 1981-03-31 NL NL8101594A patent/NL8101594A/en not_active Application Discontinuation
- 1981-03-31 DD DD81228774A patent/DD157700A5/en unknown
- 1981-03-31 ES ES501396A patent/ES501396A0/en active Granted
- 1981-03-31 CS CS812393A patent/CS221292B2/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH648340A5 (en) | 1985-03-15 |
| IE51127B1 (en) | 1986-10-15 |
| CA1160252A (en) | 1984-01-10 |
| AU6890381A (en) | 1981-10-08 |
| CS221292B2 (en) | 1983-04-29 |
| SU1034610A3 (en) | 1983-08-07 |
| JPS56151790A (en) | 1981-11-24 |
| PL230427A1 (en) | 1981-11-13 |
| IE810602L (en) | 1981-09-30 |
| ES8202776A1 (en) | 1982-02-16 |
| RO84498B (en) | 1984-08-30 |
| BR8101872A (en) | 1981-10-06 |
| AU550088B2 (en) | 1986-03-06 |
| FR2479186B1 (en) | 1982-11-26 |
| YU82881A (en) | 1983-02-28 |
| IT8021068A0 (en) | 1980-03-31 |
| DD157700A5 (en) | 1982-12-01 |
| HU192065B (en) | 1987-05-28 |
| FR2479186A1 (en) | 1981-10-02 |
| ES501396A0 (en) | 1982-02-16 |
| LU83265A1 (en) | 1981-10-29 |
| BE888150A (en) | 1981-09-28 |
| DE3112277A1 (en) | 1982-03-18 |
| SE8101977L (en) | 1981-10-01 |
| YU41038B (en) | 1986-10-31 |
| NZ196606A (en) | 1984-03-16 |
| NO811022L (en) | 1981-10-01 |
| NL8101594A (en) | 1981-10-16 |
| RO84498A (en) | 1984-06-21 |
| GB2072668B (en) | 1984-03-28 |
| DK137281A (en) | 1981-10-01 |
| IT1140794B (en) | 1986-10-10 |
| DE3112277C2 (en) | 1985-05-02 |
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