DE830870C - Rust-preventing additives for non-gaseous hydrocarbon oils - Google Patents
Rust-preventing additives for non-gaseous hydrocarbon oilsInfo
- Publication number
- DE830870C DE830870C DEN1084A DEN0001084A DE830870C DE 830870 C DE830870 C DE 830870C DE N1084 A DEN1084 A DE N1084A DE N0001084 A DEN0001084 A DE N0001084A DE 830870 C DE830870 C DE 830870C
- Authority
- DE
- Germany
- Prior art keywords
- rust
- gaseous hydrocarbon
- polycarboxylic acid
- oil
- solvent
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
- C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
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- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/02—Water
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Description
(WiGBl. S. 175)(WiGBl. P. 175)
AUSGEGEBEN AM 7. FEBRUAR 1952ISSUED FEBRUARY 7, 1952
N 1084 VIaI 48 dN 1084 VIaI 48 d
Die Erfindung bezieht sich auf antikorrodierende Kohlenwasserstoffprodukte, wie Benzin, Dieselöl, Schmieröl, Spülöl, Albinoasphaltüberzüge usw., welche geringe Mengen bestimmter korrosionsverhindernder Stoffe enthalten.The invention relates to anti-corrosive hydrocarbon products such as gasoline, diesel oil, Lubricating oil, flushing oil, albino asphalt coatings, etc., which contain small amounts of certain corrosion preventive Contain substances.
Es ist bekannt, daß Polycarbonsäuren von verhältnismäßig hohem Molekulargewicht sowie gewisse Oxycarbonsäuren, in geringen Mengen in Kohlenwasserstoffölen gelöst, diesen antikorrodierende Eigenschaften verleihen. Die gesättigten Säuren sind infolge ihrer größeren Stabilität gegenüber Oxydation vorzuziehen, so daß Schutzschichten von längerer aktiver Dauer entstehen. Die beste Wirkung zeigen alkylierte Bernsteinsäuren, die insgesamt mehr als1 i6 Kohlenstoff a tome und vorzugsweise 20 oder mehr Kohlenstoff a tome besitzen (vgl. die amerikanische Patentschrift 2 133734).It is known that polycarboxylic acids of relatively high molecular weight and certain oxycarboxylic acids, dissolved in small amounts in hydrocarbon oils, impart anti-corrosive properties to them. The saturated acids are to be preferred because of their greater stability to oxidation, so that protective layers with a longer active duration are created. The best effect show alkylated succinic acids, which total more than 1 tome i6 carbon a and preferably 20 or more carbon a tome (cf.,. United States Patent No. 2 133 734).
öle, die Polycarbonsäuren oder Hydroxylpolycarbonsäuren enthalten, bilden aber auf Eisenmetallen selbst nach langem Eintauchen! und mit Zirkulie- ao reni keine Schutzschicht, wenn das öl völlig trocken und kein freies Wasser oder ein anderer stark polarer Stoff zugegen; ist. Augenscheinlich muß das Antikorrosionsmittel von. einer polaren Grenzschicht angezogen werden, die von Wasser und anderen as stark polaren Stoffen durch Adsorption an der Metalloberfläche gebildet wird. Möglicherweise erleichtern die polarem Stoffe auch die Bildung einer wasserabstoßenden, in den ölen nahezu unlöslichen Seife aus den Säuren mit dem an der Metalloberfläche anhaftenden Oxydifilm, der selbst an frischpolierten Eisenrnetallflächen vorhanden ist.oils, the polycarboxylic acids or hydroxylpolycarboxylic acids contain, but form on ferrous metals even after long immersion! and with circula- ao reni no protective layer when the oil is completely dry and no free water or any other strongly polar substance present; is. Apparently it must Anti-corrosion agent from. be attracted to a polar boundary layer by water and other as strongly polar substances is formed by adsorption on the metal surface. Possibly make it easier The polar substances also form a water-repellent, almost insoluble in oils Soap from the acids with the oxide film adhering to the metal surface, which itself is on freshly polished Iron metal surfaces is present.
Es ist bekannt, daß Schmieröle bei längerem Gebrauch einen Schlamm bilden, der sich germ anIt is known that lubricating oils with prolonged use form a sludge that germs itself
metallischen Flächen absetzt und die Schmierung bindert. Es ist oft schwierig, diesen ölschlamm aus der Maschine durch einfaches Spülen wirkungsvoll zu entfernen. Überdies ist die Schlammabsetzung häufig1 vom Korrosion begleitet, und nach der Entfernung bleibt oft eine gewisse Menge eines mehr oder weniger lockeren Rostes zurück.metallic surfaces and the lubrication binds. It is often difficult to effectively remove this oil sludge from the machine by simply flushing it. Moreover, the sludge removal is often accompanied by corrosion 1, and after removal often a certain amount remains a more or less loose grate.
Es wurde nun gefunden, daß nicht nur Metallteile wirksamer gegen Korrosion geschützt werdenIt has now been found that not only metal parts are protected more effectively against corrosion
ίο können, sondern auch niedergeschlagener Schlamm mit mindestens einem Teil des gebildeten Rostes besser durch Spülen entfernt werden kann, wenn ein Kohlenwasserstoffprodukt nach der Erfindung verwendet wird. Erfindungsgemäß wird nicht gasförmigen Kohlenwasserstoffen nicht nur in an sich bekannter Weise eine verhältnismäßig geringe Menge von Polycarbonsäuren hohen Molekulargewichts zugesetzt, sondern· auch ein1 geringer Anteil eines organischen Stoffes, der in Kohlenwasser-ίο can, but also precipitated sludge with at least a part of the rust formed can be better removed by flushing if a hydrocarbon product according to the invention is used. According to the invention the non-gaseous hydrocarbons is not only in a conventional manner was added a relatively small amount of polycarboxylic acids, high molecular weight, but also a 1 · small proportion of an organic substance, of the hydrocarbons in
ao stoffölen löslich ist und sich in Wasser wenigstens teilweise, nämlich mindestens zu 10 Vo, löst. Dieser Stoff wird weiterhin) der Kürze halber Lösungsmittel genannt werden.ao substance oils is soluble and in water at least partially, namely at least 10 Vo, dissolves. This substance is still a solvent for the sake of brevity to be named.
Es hat sich gezeigt, daß die Kohlenwasserstoffe infolge der Anwesenheit des Lösungsmittels fähig sind, mindestens geringe Mengen Wasser zu lösen, so daß die Polycarbonsäuren Schutzüberzüge auf Metallflächen' bilden können, ohne daß die Gegenwart einer gesonderten wässerigen Schicht notwendig ist.It has been shown that the hydrocarbons are capable due to the presence of the solvent are to dissolve at least small amounts of water, so that the polycarboxylic acids on protective coatings Metal surfaces' can form without the need for the presence of a separate aqueous layer is.
In> vielen Fällen' kann es erwünscht sein, den1 Produkten gemäß der Erfindung gleich zu Beginn geringe Mengen Wasser zuzufügen, z. B. 0,05 bis 1 °/o, weil dadurch die Bildung des Schutzfilms beschleunigt wird.In> many cases it may be desirable 'to add the 1 products according to the invention at the very beginning small quantities of water, for. B. 0.05 to 1%, because this accelerates the formation of the protective film.
Es ist eine wohlbekannte Erscheinung, daß sich in Benzinfäs'serni bei längerer Lagerung in tropischem Klima große Mengen Wasser ansammeln, welche starke Verrostungen verursachen;. Wenn dem Benzin die obengenannten Polycarbonsäuren zugesetzt werden, wird die Korrosion wirksam verhindert, wenn die Fässer so lange bewegt werden, als zur Bildung des Schutzfilms notwendig ist. Diese Zeit kann., von verschiedenen Umständen abhängig, in der Größenordnung von einigen Tagen oder selbst Wochen liegen). Wenn jedoch das Benzin außerdem eine geringe Menge Wasser gelöst enthält, was durch Anwesenheit eines Zusatzstoffes ermöglicht wird1, so kann diese Zeit auf die Größenord1-nung vom Sekundenbruchteilen verringert werden.It is a well-known phenomenon that large amounts of water accumulate in gasoline drums when they are stored for long periods in a tropical climate, causing severe rusting. When the above-mentioned polycarboxylic acids are added to gasoline, corrosion is effectively prevented if the drums are moved for as long as is necessary to form the protective film. This time can be on the order of a few days or even weeks, depending on various circumstances). If, however, also contains a small amount of dissolved water, the fuel, which is made possible by the presence of an additive 1, so this time can be reduced from 1 -nung fractions of a second to the size Nord.
Die Menge der verschiedenen Bestandteile im denThe amount of the various ingredients in the
Kohlenwasserstoffprodukten gemäß der Erfindung und die Art des Lösungsmittels hängt einigermaßen von dem Verwendungszweck ab. Treibstoffe, wie Benzin und! Dieselöl, benötigen nur eine geringe Menge der Polycarbonsäuren) und eine verhältnismäßig geringe Menge der Lösungsmittel. Diese Stoffe sollen vorzugsweise innerhalb desselben Bereichs sieden wie der Treibstoff. So kann, ein Benzintreibstoff zusammengesetzt sein aus 95 bis über 99 °/o Benzin, 0,001 bis 0,1 Vo Polycarbonsäure und 0,1 bis 5 °/o einesi Lösungsmittels. Als Lösungsmittel kommen besonders Dialkyläther, Ketone und Alkohole in Betracht, die im Benzintereich sieden, z. B. Diisopropyläther, Dioxan, Aceton, Äthylalkohol und deren niedrigere Homologen. Einige dieser Stoffe können auch eine Erhöhung der Octanzahl bewirken, wenn sie in hinreichenden Mengen vorhanden sind. Größere Mengen der Polycarbonsäuren führen oft zur Bildung harzartiger Stoffe und sind daher zu vermeiden.Hydrocarbon products according to the invention and the type of solvent depends somewhat on the intended use. Fuels, such as gasoline and! Diesel oil, only require a small amount Amount of polycarboxylic acids) and a relatively small amount of solvents. These Substances should preferably boil within the same range as the fuel. So can, a Petrol may be composed of 95 to over 99 per cent gasoline, 0.001 to 0.1 vol of polycarboxylic acid and 0.1 to 5% of a solvent. as Particularly suitable solvents are dialkyl ethers, ketones and alcohols, which are used in the gasoline sector boil, e.g. B. diisopropyl ether, dioxane, acetone, ethyl alcohol and their lower homologues. Some of these substances can also cause an increase in the octane number if they are in sufficient quantities Quantities are available. Larger amounts of the polycarboxylic acids often lead to the formation of resinous ones Substances and are therefore to be avoided.
Dieselöle sollen wie Benzine 0,001 bis 0,1 °/o Polycarbonsäure und 0,1 bis 5 °/o eines Lösungsmittels enthalten, vorzugsweise eines Lösungsmittels, der die Octanzahl verbessert, wie niedrige Nitroparaffine, Cj-Cg-Nitrate oder Nitrite, Nitromercaptane mit 2 bis 5 Kohlenstoffatomen, Peroxyde, wie Benzoylperoxyd und Peroxyde aliphatischer Ketone mit z. B. 3 bis 6 Kohlenstoffatomen. Es können auch wie bei Benzin Äther, Alkohole oder Ketone, die im richtigen Bereich sieden., angewendet werden,. Durch diese Verbindungen werden aber die Octanzahlen nicht wesentlich beeinflußt.Diesel oils, like gasoline, should be 0.001 to 0.1 per cent Polycarboxylic acid and 0.1 to 5% of a solvent contain, preferably a solvent that improves the octane number, such as low Nitroparaffins, Cj-Cg nitrates or nitrites, nitromercaptans with 2 to 5 carbon atoms, peroxides such as benzoyl peroxide and peroxides more aliphatic Ketones with z. B. 3 to 6 carbon atoms. As with gasoline, it can also be ether, alcohol or Ketones that boil in the correct range., Are used. Through these connections, however, the Octane numbers not significantly affected.
Schmieröle benötigen oft größere Mengen als Treibstoffe, sowohl der Polycarbonsäuren als auch der Lösungsmittel, da sie» normalerweise während ihrer Benutzung dem Einfluß von Wärme unterworfen sind, und zwar innig gemischt mit Luft; diese Bedingungen führen sowohl zur Bildung von löslichen korrodierenden Produkten als auch von unlöslichem Schlamm. Es ist eine beträchtliche Variierung der Zusammensetzung eines Schmieröls zulässig. So können Schmieröle gemäß der Erfindung aus 80 bis 99 °/o eines Schmieröls, 0,001 bis 1,0 °/o einer Polycarbonsäure und 0,1 bis 20 °/o eines geeigneten Lösungsmittels bestehen, obwohl für die übliche Maschinenschmierung vorzugsweise die Menge des Lösungsmittels unter 5 Gewichtsprozent gehalten wird. Aus praktischen Gründen werden vorzugsweise oberhalb 1500 siedende Stoffe gewählt. Dazu gehören z. B. Glykole mit 6 oder mehr Kohlenstoffatomen, Diglykole, Triglykole, Ätheralkohole, vorzugsweise mit nicht mehr als 2 OH-Radikalen, insbesondere Glykolmonoalkyläther, Diglykolmonoalkyläther, z. B. die Carbitole, Glycerinmono- oder -diätbier mit 6 oder mehr Kohlenstoffatomen, Monoester von Glykol oder Glycerin usw.Lubricating oils often require larger quantities than fuels, both of the polycarboxylic acids and the solvents, since they "are normally subjected to the influence of heat during their use, and indeed intimately mixed with air; these conditions lead to the formation of both soluble corrosive products and insoluble sludge. Considerable variation in the composition of a lubricating oil is allowable. Thus, lubricating oils according to the invention can consist of 80 to 99% of a lubricating oil, 0.001 to 1.0% of a polycarboxylic acid and 0.1 to 20% of a suitable solvent, although the amount of solvent is preferred for normal machine lubrication is kept below 5 percent by weight. For practical reasons, preferably be chosen above 150 0-boiling substances. These include B. glycols with 6 or more carbon atoms, diglycols, triglycols, ether alcohols, preferably with no more than 2 OH radicals, in particular glycol monoalkyl ethers, diglycol monoalkyl ethers, e.g. B. the carbitols, glycerine mono- or diet beer with 6 or more carbon atoms, monoesters of glycol or glycerine, etc.
Die Spülöle gemäß der Erfindung benötigen üblicherweise Mengen zwischen etwa 0,01 und 0,25 °/o Polycarbonsäure und etwa 2 bis. 20% im Lösungsmittel. Für Spülöle werden vorzugsweise verhältnismäßig hoch siedende Kohlenwasserstofffraktionen benutzt, welche vorzugsweise mindestens 50 °/o Aromaten besitzen und vorzugsweise spezifische Dispersionen über etwa 200, bestimmt nach der Methode vom Fuchs und Andersen, haben (Ind.Engl.Chem. 29, 319, März 1937). Sicherheitshalber sand verhältnismäßig hohe Flamm- und Brennpunkte erwünscht. Zum Beispiel können gespaltene oder andere hoch siedende Destillate verwendet werden, wenn sie aromatenreich sind.The flushing oils according to the invention usually require amounts between about 0.01 and 0.25% polycarboxylic acid and about 2 to. 20% in Solvent. Relatively high-boiling hydrocarbon fractions are preferred for flushing oils used, which preferably have at least 50% aromatics and preferably specific Have dispersions over about 200, determined by the method von Fuchs and Andersen (Ind.Engl.Chem. 29, 319, March 1937). To be on the safe side sand relatively high flash points and focal points are desirable. For example can split or other high-boiling distillates can be used if they are rich in aromatics.
Die bei Spülölen geeigneten Lösungsmittel sind im allgemeinen die gleichen, die bei Schmierölen verwendbar sind. Im allgemeinen benötigen die Spülöle aber keinen Zusatz von Wasser zwecks Aktivierung der Polycarbonsäure.The solvents useful with flushing oils are generally the same as those used with lubricating oils are usable. In general, however, the flushing oils do not require the addition of water Activation of the polycarboxylic acid.
ölschlamm ist üblicherweise stark wasserhaltig.Oil sludge usually contains a lot of water.
Das Lösungsmittel mimmt Wasser aus dem Schlamm auf und macht ihn dadurch in dem aromatischen Spülöl löslich. Auch aktiviert das Lösungsmittel, wie ol>en beschrieben, die Polycarbonsäure.The solvent absorbs water from the sludge, making it into the aromatic one Soluble flushing oil. As described in ol> en, the solvent also activates the polycarboxylic acid.
Bei bestimmten Maschinen, wie Dampfturbinen, kondensiert sich häufig Wasser in dem Schmiersystem. Mindestens ein Teil dieses Wassers bleibt l>eim Abziehen des Schmieröls in Vertiefungen zu-In certain machines, such as steam turbines, water often condenses in the lubrication system. At least part of this water remains in the depressions when the lubricating oil is drawn off.
to rück. Wenn mit Spülöl gemäß der Erfindung gespült wird, mischt sich das Wasser mit dem öl und aktiviert die Polycarbon'säure.to back. When flushed with flushing oil according to the invention the water mixes with the oil and activates the polycarboxylic acid.
Albinoasphaltüberzüge können verhältnismäßig große Mengen an Polycarbonsäuren erfordern, die bis zu 10 Gewichtsprozent des Albinoasphalts betragen können; die Mengen der Lösungsmittel müssen- hinreichend sein zur Lösung der notwendigem aktivierenden Wassermengen und können je nach dem Umständen von 0,1 bis 90% in bezugAlbino asphalt coatings can require relatively large amounts of polycarboxylic acids, which can be up to 10 percent by weight of the albino asphalt; the amounts of solvents must be sufficient to solve the necessary activating amounts of water and can depending on the circumstances from 0.1 to 90%
ao auf das Gewicht des Albinoasphalts variieren.ao vary based on the weight of the albino asphalt.
Die Kohlenwasserstoffprodukte gemäß der Erfindung können gewünschtenfalls andere Zusatzmittel enthalten., um auch andere Eigenschaften, als. die Korrosionsverhinderung zu verbessern.The hydrocarbon products according to the invention can, if desired, contain other additives included. to include properties other than. improve corrosion prevention.
Die Erfindung wird durch die folgenden Beispiele veranschaulicht.The invention is illustrated by the following examples.
Ein wie oben beschrieben aus Spaltanlagekoks abgeblasenesi öl wurde mit 70 kg o.8°/oiger H2 S O4 pro Kubikmeter öl behandelt. Nach dem Abtrennen des Öls von der Säure und Behandeln mit Bleicherde wurde es im Vakuum destilliert unter Erzeugung eines sog. Neutralöls, das ungefähr 80% des ursprünglich behandelten Öls darstellte. Dieses Neutralöl wurde zur Herstellung eines Spülöls, benutzt, das aus etwa 95 Gewichtsprozent Neutralöl, etwa 5 Gewichtsprozent Diäthylenglykolmonobutyläther und 0,01 % einer Alkylbernsteinsäure mit 22 Kohlenstoffatomen bestand. Diese Mischung wurde durch das Schmiersystem einer Dampfturbine, die schwer verschlammt war, 30 Minuten hindurchgeschickt. An oil blown from cracking plant coke as described above was treated with 70 kg of 0.8% H 2 SO 4 per cubic meter of oil. After the oil had been separated from the acid and treated with fuller's earth, it was distilled in vacuo to produce a so-called neutral oil, which represented approximately 80% of the oil originally treated. This neutral oil was used to produce a flushing oil, which consisted of about 95 percent by weight of neutral oil, about 5 percent by weight of diethylene glycol monobutyl ether and 0.01% of an alkyl succinic acid having 22 carbon atoms. This mixture was passed through the lubrication system of a steam turbine that was heavily silted up for 30 minutes.
Das abgezogene Spülöl führte im wesentlichen den? gesamten1 Schlamm und eine große Menge Rost fort. Das in Vertiefungen angesammelte und am den Wandungen anhaftende Spülöl wurde durch ein Verdrängungsöl entfernt. Das Schmiersystem wurde mit Turbinenöl gefüllt, und es wurden nach kurzer Laufzeit Proben aus dem ölbehälter analysiert. Das öl zeigte nur geringe Verunreinigung.The flushing oil withdrawn essentially led to the? entire 1 mud and a large amount of rust. The flushing oil that had accumulated in depressions and adhering to the walls was removed by a displacement oil. The lubrication system was filled with turbine oil and samples from the oil tank were analyzed after a short run time. The oil showed little contamination.
Ein Spülöl der gleichen Zusammensetzung wie das öl des Beispiels 1 wurde zur Reinigung des. Ölbehälters im Boden des Getriebekastens eines Turbogenerators verwendet. Das Spülöl wurde mittels einer Hilfspumpe dem ölbehälter des Getriebekastens zugeführt und aus ihm abgezogen: unter Einschalten eines Filters und Dampferhitzers. Das Turbinenreinigungsöl wurde aus1 dem Kasten abgezogen und der Rest des Reimigungsöls durch ein Verdrängungsöl entfernt. Der Getriebekasten wurde mit frischem Schmiermittel gefüllt und der Turbogenerator wieder in Tätigkeit gesetzt.A flushing oil of the same composition as the oil of Example 1 was used to clean the oil tank in the bottom of the gear box of a turbo generator. The flushing oil was fed to the oil tank of the gearbox by means of an auxiliary pump and withdrawn from it: with switching on a filter and steam heater. The turbine cleaning oil was withdrawn from 1 of the box and the remainder of the cleaning oil was removed by a displacement oil. The gear box was filled with fresh lubricant and the turbo generator started up again.
Die Reinigung war so vollständig, daß die endgültige ölcharge ihre Grenzschiichtspannung gegenüber Wasser während' vieler Betriebsstundem nicht änderte, was die Abwesenheit von öllöslichen Verunreimigungeni beweist.The purification was so complete that it was definitive oil charge their boundary layer tension with respect to water during many hours of operation changed what the absence of oil-soluble impuritiesi proves.
Claims (16)
Applications Claiming Priority (1)
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US412836A US2334158A (en) | 1941-09-29 | 1941-09-29 | Rust-preventive composition |
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DE830870C true DE830870C (en) | 1952-02-07 |
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DEN1084A Expired DE830870C (en) | 1941-09-29 | 1950-06-17 | Rust-preventing additives for non-gaseous hydrocarbon oils |
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-
1941
- 1941-09-29 US US412836A patent/US2334158A/en not_active Expired - Lifetime
-
1942
- 1942-11-11 GB GB15930/42A patent/GB570952A/en not_active Expired
-
1950
- 1950-06-17 DE DEN1084A patent/DE830870C/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
US2334158A (en) | 1943-11-09 |
GB570952A (en) | 1945-07-31 |
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