US2385363A - Solidified normally liquid hydrocarbons - Google Patents
Solidified normally liquid hydrocarbons Download PDFInfo
- Publication number
- US2385363A US2385363A US435170A US43517042A US2385363A US 2385363 A US2385363 A US 2385363A US 435170 A US435170 A US 435170A US 43517042 A US43517042 A US 43517042A US 2385363 A US2385363 A US 2385363A
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- US
- United States
- Prior art keywords
- alcohol
- hydrocarbon
- reaction
- rosin
- saponification
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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
- C10L7/00—Fuels produced by solidifying fluid fuels
- C10L7/02—Fuels produced by solidifying fluid fuels liquid fuels
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/924—Significant dispersive or manipulative operation or step in making or stabilizing colloid system
- Y10S516/927—Significant dispersive or manipulative operation or step in making or stabilizing colloid system in situ formation of a colloid system making or stabilizing agent which chemical reaction
Definitions
- This invention relates to new and useful improvements in solidified normally liquid hydrocarbons.
- the normally liquid hydrocarbons in accordance with the invention are of the combustible type and preferably of the combustible fuel type.
- hydrocarbons for instance, a petroleum distillate.
- Another example is a mixture of hydrocarbons of the benzene series.
- hydrocarbons as used for fuel ordinarily contain numerous hydrocarbons, the term hydrocarbons as used herein includes the limiting case in which only one hydrocarbon is present.
- a-normally liquid hydrocarbon I may, for instance, use gasoline, although I prefer a petroleum distillateof closer boiling point.
- benzol or a light coal tar distillate consisting predomi-' nantly of benzol homologues may be used.
- normally liquid hydrocarbons in accordance with my invention are preferably for ordinary use readily inflammable and preferentiallythen possess a flash point not substantially above normal substantially dry pulverulent form, in the presence of a suitable alcohol not substantially in excess of 3% calculated on the amount of hydrocarbon present in the final product.
- the saponiflcation reaction may be either one of acid neutralization or of double decomposition.
- the saponification agent should be maintained in suspension during the reaction, 1. e., no appreciable segregation of suspended particles should occur. This, as a rule, may be accomplished by asitation or by the procurement of finest dispersion of saponification agent in the hydrocarbon to be solidified and preferably with the aid of a suitable dispersion device such asv a colloid mill, ball mill or the like.
- the product obtained when the saponification reaction is-permitted to proceed in at least the last stages thereof while the reaction mix is in substantially quies- 5 cent condition possesses superior characteristics.
- the temperature requirements may vary.- In some cases, a temperature of about 40 C. may sumce, while in other cases higher temperatures must be 2 resorted to. In most cases, once the saponiflcation reaction has been satisfactorily initiated the heating may be discontinued. In some cases, it is of advantage to initiate or expedite the saponification reaction by heating the hydrocarbon solution containing the'reactants to a temperature of above normal or alternatively procure the mixing of the reactants at such'temperature.
- the temperature requirements may vary.- In some cases, a temperature of about 40 C. may sumce, while in other cases higher temperatures must be 2 resorted to. In most cases, once the saponiflcation reaction has been satisfactorily initiated the heating may be discontinued. In some cases, it is of advantage to initiate or expedite the saponification reaction by heating the hydrocarbon solution containing the'reactants to a temperature of above normal or alternatively procure the mixing of the reactants at such'temperature.
- the temperature requirements may vary.- In some cases, a temperature
- the organic compound of the aforementioned type in accordance with the invention may comprise either a resin acid salt or a ireerosin acid, of, for instance, the type of 'abietic acid. If the same is a free acid, the saponiflcation reaction is one of neutralization of the acid with the saponification agent. On the other hand, if the same is a salt, the saponiflcation reaction is one 40 of double decomposition between the resin add salt and the saponiflcation agent. In many instances, a commercial form 01' rosin acid may be used such as, for instance, rosin.
- the saponiflcation agent in accordance with my invention may be any agent capable of neutralizing or entering into a metathetical reaction with the rosin or rosin acid, as the case may be, present in the hydrocarbon solution.
- Good re-- sults are preferably obtained with hydroxides and alcoholates and suitable saponifl'ca'tion agents oi this type are, for example, sodium hydroxide, sc dium alcoholates and thelike.
- This may be accomplished by either dispersing the dry saponification agent as such in the hydrocarbon solution of the rosin acid or by first preparing a fine dispersion of such saponification agent in substantially dry form in a part of the total hydrocarbon ultimately to be solidified and adding such dispersion to the other part oi such hydrocarbon in which the rosin acid has been dissolved. It is also sometimes of advantage and desirable to initiate or expedite the saponification reaction by passing the reaction mix through a colloid mill or other device for producing finest dispersion.
- Such dispersion defor instance, the simple alcohols of the aliphatic series, such as methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, and the like alcohols.
- Examw ples of suitable polyhydric alcohols are, for instance, the glycols.
- the alcoholate formation may be accomplished by the dissolution of a, suitable metal such as metallic sodium in the alcohol.
- the alcohol may be added either-before or after the addition of sapon'iiication agent.
- the reaction mix should be oneness both these hydrocarbon products to procure so- .lidirlcation. This, as is well understood, oifers certain advantages for industrial production.
- the amount of reagents used within the practical application of my invention should be preferably so adjusted that the organic compound to 10% of rosin acid or salt will accomplishthis .result.
- the saponification agent should be present in amount s'uflicient to accomplish the saponiflcation, which as a rule requires in excess of stoichiometric amounts. When using alcoholates containing crystal alcohol, care should be taken that the alcohol content is considered in calculating the required amount of saponification agent.
- the amount of alcohol introduced as crystal alcohol when using alco-, holates is sufllcient to expedite the saponification reaction to the desired extent.
- care shouldbe taken that the total amount of free alcohol ultimately present in the solidified product upon completion of the saponification reaction is not substantially pension upon discontinuing the agitation.
- Agi- I the alcohol while another portion is prepared containing the reaction products as, for instance, a suitable rosin and finely dispersed saponification agent.
- the alcohol to be used in accordance with the invention for expediting the saponification reaction or bringing the same to the desired completion is preferably a primary aliphatic alcohol.
- the amount of this alcohol to be used may vary with the particular alcohol and depends, inter alia, upon considerations of solubility.
- the alcohol should be one in which the saponii'lcation agent is at least limitedly soluble. I prefer to use a substantially water soluble alcohol of the aliphatic series such as methyl or ethyl alcohol
- the procedure in accordance with the invention is exemplified in the followingexample.
- Example A 5% rosin solution in a petroleum hydrocarbon cut of a boiling range of to 210 F. was prepared. 1.88% by weight of methyl alcohol and 1.5% by weight of substantially anhydrous sodium hydroxide were added to the rosin solution.
- the sodium-hydroxide was added in finely pulverized form and kept in fine suspension in the rosin solution by means of agitation, Pulverization was carried out mechanically in a mortar in the presence-of a portion of. the hydrocarbon. Agitation was maintained until the gel formation had proceeded to a point of desired viscosity to prevent segregation of particles of saponification agent.
- the reaction mass was then poured into fuel containers within which it solidified without This is critical in view of the any further manipulation.
- the one obtained permitting the saponification' to go to completion with the mix in a substantially quiescent state is softer, less homogeneous and compact.
- the alcohol instead of adding, as set forth in the hereinabove recited example, the alcohol to the rosin solution, it is possible and sometimes of advantage to add the alcohol to the rosin solution v after the saponification agent has been dispersed therein. This practice is particularly recommended in cases, where, as hereinabove outlined, the viscosity of therosin solution is so coordinated to the particle size of suspended saponifica- .tion agent that a substantially stable dispersion maintains.
- Such a rosin solution containing dispersed saponification agent may be left quiescent or may even be stored for lesser or greater periods of time depending upon its stability, to be drawn upon as required.
- a, solution may serve asa stock solution.
- the addition of the required amount of alcohol to such solution, with or without heating as may be necessary, will then cause without the necessity of heating the reaction mix.
- the productsobtained in accordance with the invention are substantially homogeneous and can be cut with a knife and handled as ordinary solids.
- the products will not liquefy when subject to raised temperatures and will burn without melting.
- the products are further characterized by the fact that the normally liquid hydrocarbon materials which they contain may be recovered in substantially unadulterated form by the application of pressure, centrifugal manipulations, distillation, or the like.
- the hydrocarbon material may be recovered from the products solidified in accordance with the invention, by separation with the aid of suitable solvent extraction.
- the extracting solvent is preferably one in which the hydrocarbon is but limitedly soluble or substantially individed by the total volumeof the components.
- the solidified products contain a high volume percentage of hydrocarbon material.
- Method for solidifying normally liquid inflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon with a saponification agent-of the group consisting of sodium hydroxideand sodium alcoholates suspended in said hydrocarbon in substantially dry pulverulent form,- of the type reactable with said rosin to thereby form a voluminous metallic soap gel from limitedly soluble to insoluble in said hydrocarbon, in the presence of an aliphatic substantially water-soluble alcohol in amount-not substantially in excess of 3% of the hydrocarbon.
- Method for solidifying normally liquid inflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon, in the presence of a substantially water soluble aliphatic alcohol, with sodium hydroxide suspended in said hydrocarbon in substantially dry pulverulent 'form, said alcohol being present not substantially in excess of 3% of the hydrocarbon.
- Method for solidifying normally liquidinflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon, in the presence of a substantially water soluble aliphatic alcohol of substantiallynot more than two carbon atoms, with sodium hydroxide, suspended in said hydrocarbon in. substantially dry pulverulent form, agitating the mixat least until the viscosity imparted thereto by a portion of the rosin soap gel formed is suflicient to maintain the so dium hydroxide in suspension while said mix is quiescent, discontinuing agitation and permitting the mix to remain substantially quiescent'during at least the last stages of the reaction-said alco- .hol being present in amount not substantially in excess of 3% of the hydrocarbon.
- Method for solidifying normally liquid inflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon, in the presence of a substantially water soluble aliphatic alcohol having substantially notin excess of two carbon atoms, with sodium hydroxide, suspended in said hydrocarbon in substantially dry pulverulent form and agitating the mix at least until the substantial completion of the saponiflcation reaction, said-alcohol being present in amount not substantially in excess of 3% of the by carbon.
Description
Patentedsept. 25, 1945 I ,umrso SOLIDIFIED NORMALLY LIQUID HYDBOCARBONS Albert Joseph Lallbertc; Naugatuck, coma. as-
signor to Safety-Fuel, Incorporated, West Cheshire, Conn., a corporation of Qonnecticut No Drawing.-
6 Claims.
This invention relates to new and useful improvements in solidified normally liquid hydrocarbons.
The normally liquid hydrocarbons in accordance with the invention are of the combustible type and preferably of the combustible fuel type.
One example, is for instance, a petroleum distillate. Another example is a mixture of hydrocarbons of the benzene series. Although such normally liquid hydrocarbons as used for fuel ordinarily contain numerous hydrocarbons, the term hydrocarbons as used herein includes the limiting case in which only one hydrocarbon is present. As a-normally liquid hydrocarbon, I may, for instance, use gasoline, although I prefer a petroleum distillateof closer boiling point. Also benzol or a light coal tar distillate consisting predomi-' nantly of benzol homologues may be used. The
normally liquid hydrocarbons in accordance with my invention are preferably for ordinary use readily inflammable and preferentiallythen possess a flash point not substantially above normal substantially dry pulverulent form, in the presence of a suitable alcohol not substantially in excess of 3% calculated on the amount of hydrocarbon present in the final product.
The saponiflcation reaction may be either one of acid neutralization or of double decomposition. The saponification agent should be maintained in suspension during the reaction, 1. e., no appreciable segregation of suspended particles should occur. This, as a rule, may be accomplished by asitation or by the procurement of finest dispersion of saponification agent in the hydrocarbon to be solidified and preferably with the aid of a suitable dispersion device such asv a colloid mill, ball mill or the like. Alternatively, segregation of suspended particles may be avoided'by thev formation of a portion of the soap gel to a point at which the viscosity imparted to the mix by the gel is sufficient to substantially maintain the particles in suspension, in which case agitation may be discontinued once the viscosity of the mixand the particle size of suspended saponiflcation agent Application March 18, 1942, Serial No. 435,170
are thusly coordinated. In general, the product obtained when the saponification reaction is-permitted to proceed in at least the last stages thereof while the reaction mix is in substantially quies- 5 cent condition possesses superior characteristics.
inter alia, with respect to homogeneity and compactness, as compared with a product obtained from a reaction mix agitated during the entire saponification reaction or at least during the last stages thereof. Though the more compact produst is normally preferred, special considerations and circumstances may make it desirable to procure a product of the type obtained with agitation during the last stages of the saponiflcation re- 1 action.
In some cases it is of advantage to initiate or expedite the saponification reaction by heating the hydrocarbon solution containing the'reactants to a temperature of above normal or alternatively procure the mixing of the reactants at such'temperature. Depending upon the reactants used, the temperature requirements may vary.- In some cases, a temperature of about 40 C. may sumce, while in other cases higher temperatures must be 2 resorted to. In most cases, once the saponiflcation reaction has been satisfactorily initiated the heating may be discontinued. In some cases, it
may be of advantage to continue the heating until the substantial completion of the saponiflcation reaction.
The organic compound of the aforementioned type in accordance with the invention may comprise either a resin acid salt or a ireerosin acid, of, for instance, the type of 'abietic acid. If the same is a free acid, the saponiflcation reaction is one of neutralization of the acid with the saponification agent. On the other hand, if the same is a salt, the saponiflcation reaction is one 40 of double decomposition between the resin add salt and the saponiflcation agent. In many instances, a commercial form 01' rosin acid may be used such as, for instance, rosin.
Wherever reference is made herein to the term I rosin acid the same is used generically, and is intended to embrace any one ormore rosin acids either as such, or in their commercial. form or iorms. The saponiflcation agent in accordance with my invention may be any agent capable of neutralizing or entering into a metathetical reaction with the rosin or rosin acid, as the case may be, present in the hydrocarbon solution. Good re-- sults are preferably obtained with hydroxides and alcoholates and suitable saponifl'ca'tion agents oi this type are, for example, sodium hydroxide, sc dium alcoholates and thelike.
In some cases I prefer to suspend the sapon-' ification agent in substantially anhydrous pulverulent finely dispersed form in the solution containing the organic acid with the use of a colloid mill-or other device for procuring finest dispersion. This may be accomplished by either dispersing the dry saponification agent as such in the hydrocarbon solution of the rosin acid or by first preparing a fine dispersion of such saponification agent in substantially dry form in a part of the total hydrocarbon ultimately to be solidified and adding such dispersion to the other part oi such hydrocarbon in which the rosin acid has been dissolved. It is also sometimes of advantage and desirable to initiate or expedite the saponification reaction by passing the reaction mix through a colloid mill or other device for producing finest dispersion. Such dispersion defor instance, the simple alcohols of the aliphatic series, such as methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, and the like alcohols. Examw ples of suitable polyhydric alcohols are, for instance, the glycols. The alcoholate formation may be accomplished by the dissolution of a, suitable metal such as metallic sodium in the alcohol. Whenever possible, however, such as in the case of simple aliphatic alcohols, as, for instance, methyl alcohol, ethyl alcohol, and the like, I preier to obtain alcoholate formation by adding to a strong and concentrated alcohol, a suitable solid anhydrous metal hydroxide, such as sodium hydroxide, with subsequent evaporation of excess alcohol. When proceeding in this manner, I prefor to use an alcohol concentration of in excess of 90% and preferably in excess of 95% and preferably equimolecular proportions of alcohol and hydroxide.
In accordance with the invention, from .25 to 3% alcohol and preferably from 5% to 1.5% calculated on the amount of hydrocarbon present gives satisfactory results. The alcohol may be added either-before or after the addition of sapon'iiication agent. Well agitated while the saponification reaction takes place at-least until the gel formation has reached a point as hereinabove stated at which the viscosity thereby imparted to the hydrocarbon solution is suficient to substantially maintain the dispersed saponification agent in sus- The reaction mix should be oneness both these hydrocarbon products to procure so- .lidirlcation. This, as is well understood, oifers certain advantages for industrial production.
The amount of reagents used within the practical application of my invention should be preferably so adjusted that the organic compound to 10% of rosin acid or salt will accomplishthis .result. The saponification agent should be present in amount s'uflicient to accomplish the saponiflcation, which as a rule requires in excess of stoichiometric amounts. When using alcoholates containing crystal alcohol, care should be taken that the alcohol content is considered in calculating the required amount of saponification agent.
In the majority of cases the amount of alcohol introduced as crystal alcohol when using alco-, holates is sufllcient to expedite the saponification reaction to the desired extent. In some cases, however, it may be desirable to have a relatively small amount of free alcohol, 1. e., alcohol not present in bound form, such as crystal alcohol, so as toat least initiate the saponification reaction whereby the further amounts of alcohol are liberated from the alcoholate to serve this purpose. In all cases, however, care shouldbe taken that the total amount of free alcohol ultimately present in the solidified product upon completion of the saponification reaction is not substantially pension upon discontinuing the agitation. Agi- I the alcohol while another portion is prepared containing the reaction products as, for instance, a suitable rosin and finely dispersed saponification agent. It is then only necessary to intermix in excess of 3%. fact that higher percentage contents of alcohol may impair the characteristics of the finished solidified product, as such excess alcohol content may result in a liquification or partial liquification of the roduct upon heating or when burning. The amount of alcohol present in accordance with the invention, 1. e., not appreciably in excess of about 3%, is at no time sufdcient to interfere with the efiective formation of insoluble soap gel and thus solidification of the hydrocarbon material.
The alcohol to be used in accordance with the invention for expediting the saponification reaction or bringing the same to the desired completion is preferably a primary aliphatic alcohol. The amount of this alcohol to be used may vary with the particular alcohol and depends, inter alia, upon considerations of solubility. The alcohol should be one in which the saponii'lcation agent is at least limitedly soluble. I prefer to use a substantially water soluble alcohol of the aliphatic series such as methyl or ethyl alcohol The procedure in accordance with the invention is exemplified in the followingexample.
Example A 5% rosin solution in a petroleum hydrocarbon cut of a boiling range of to 210 F. was prepared. 1.88% by weight of methyl alcohol and 1.5% by weight of substantially anhydrous sodium hydroxide were added to the rosin solution. The sodium-hydroxide Was added in finely pulverized form and kept in fine suspension in the rosin solution by means of agitation, Pulverization was carried out mechanically in a mortar in the presence-of a portion of. the hydrocarbon. Agitation was maintained until the gel formation had proceeded to a point of desired viscosity to prevent segregation of particles of saponification agent. The reaction mass was then poured into fuel containers within which it solidified without This is critical in view of the any further manipulation.
solidification proceeded rapidly.
In a further example the same procedure was .followed as hereinabove described. In this case,
the one obtained permitting the saponification' to go to completion with the mix in a substantially quiescent state, is softer, less homogeneous and compact. Instead of adding, as set forth in the hereinabove recited example, the alcohol to the rosin solution, it is possible and sometimes of advantage to add the alcohol to the rosin solution v after the saponification agent has been dispersed therein. This practice is particularly recommended in cases, where, as hereinabove outlined, the viscosity of therosin solution is so coordinated to the particle size of suspended saponifica- .tion agent that a substantially stable dispersion maintains. Such a rosin solution containing dispersed saponification agent may be left quiescent or may even be stored for lesser or greater periods of time depending upon its stability, to be drawn upon as required. Thus such a, solution may serve asa stock solution. The addition of the required amount of alcohol to such solution, with or without heating as may be necessary, will then cause without the necessity of heating the reaction mix.
The productsobtained in accordance with the invention are substantially homogeneous and can be cut with a knife and handled as ordinary solids. The products will not liquefy when subject to raised temperatures and will burn without melting. The products are further characterized by the fact that the normally liquid hydrocarbon materials which they contain may be recovered in substantially unadulterated form by the application of pressure, centrifugal manipulations, distillation, or the like. Alternatively, the hydrocarbon material may be recovered from the products solidified in accordance with the invention, by separation with the aid of suitable solvent extraction. In such case, the extracting solvent is preferably one in which the hydrocarbon is but limitedly soluble or substantially individed by the total volumeof the components.
with the. invention By reason of their density and characteristics of structure, the solidified products contain a high volume percentage of hydrocarbon material.
The foregoing description is furnished by way of illustration and not of limitation and it is, therefore, my intention that the invention be limited only by the appended claims or their equivalent wherein I have endeavored to claim broad -ly all inherent novelty.
I claim:
1. Method for solidifying normally liquid inflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon with a saponification agent-of the group consisting of sodium hydroxideand sodium alcoholates suspended in said hydrocarbon in substantially dry pulverulent form,- of the type reactable with said rosin to thereby form a voluminous metallic soap gel from limitedly soluble to insoluble in said hydrocarbon, in the presence of an aliphatic substantially water-soluble alcohol in amount-not substantially in excess of 3% of the hydrocarbon.
2. Method for solidifying normally liquid inflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon, in the presence of a substantially water soluble aliphatic alcohol, with sodium hydroxide suspended in said hydrocarbon in substantially dry pulverulent 'form, said alcohol being present not substantially in excess of 3% of the hydrocarbon.
3. Method for solidifying normally liquidinflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon, in the presence of a substantially water soluble aliphatic alcohol of substantiallynot more than two carbon atoms, with sodium hydroxide, suspended in said hydrocarbon in. substantially dry pulverulent form, agitating the mixat least until the viscosity imparted thereto by a portion of the rosin soap gel formed is suflicient to maintain the so dium hydroxide in suspension while said mix is quiescent, discontinuing agitation and permitting the mix to remain substantially quiescent'during at least the last stages of the reaction-said alco- .hol being present in amount not substantially in excess of 3% of the hydrocarbon.
4. Method according to claim 3 in which said alcohol is methyl alcohol present in amount substantially from 0.25 to 1.5% of the hydrocarbon.
5. Method for solidifying normally liquid inflammable hydrocarbons which comprises reacting a rosin solution in said hydrocarbon, in the presence of a substantially water soluble aliphatic alcohol having substantially notin excess of two carbon atoms, with sodium hydroxide, suspended in said hydrocarbon in substantially dry pulverulent form and agitating the mix at least until the substantial completion of the saponiflcation reaction, said-alcohol being present in amount not substantially in excess of 3% of the by carbon.
6. Method according to claim 5 in which said alcohol is methyl alcohol present in amount substantially from 0.25 to 1.5% of the-hydrocarbon.
ALBERT .rosEPH LAmEa'rE.
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US435170A US2385363A (en) | 1942-03-18 | 1942-03-18 | Solidified normally liquid hydrocarbons |
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US435170A US2385363A (en) | 1942-03-18 | 1942-03-18 | Solidified normally liquid hydrocarbons |
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US2385363A true US2385363A (en) | 1945-09-25 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2618536A (en) * | 1950-09-20 | 1952-11-18 | Sherwin Williams Co | Gel-type fuel and method of making same |
US3966897A (en) * | 1973-04-02 | 1976-06-29 | Marine Colloids, Inc. | Medium for use in bioassay and method of using same |
US20050230104A1 (en) * | 1998-12-07 | 2005-10-20 | Shell Oil Co. | Apparatus for expanding a tubular member |
US20070205001A1 (en) * | 2003-09-05 | 2007-09-06 | Eventure Global Technology, Llc | Expandable Tubular |
-
1942
- 1942-03-18 US US435170A patent/US2385363A/en not_active Expired - Lifetime
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2618536A (en) * | 1950-09-20 | 1952-11-18 | Sherwin Williams Co | Gel-type fuel and method of making same |
US3966897A (en) * | 1973-04-02 | 1976-06-29 | Marine Colloids, Inc. | Medium for use in bioassay and method of using same |
US20050230104A1 (en) * | 1998-12-07 | 2005-10-20 | Shell Oil Co. | Apparatus for expanding a tubular member |
US20070205001A1 (en) * | 2003-09-05 | 2007-09-06 | Eventure Global Technology, Llc | Expandable Tubular |
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