|Publication number||US3876391 A|
|Publication date||8 Apr 1975|
|Filing date||24 Aug 1971|
|Priority date||28 Feb 1969|
|Publication number||US 3876391 A, US 3876391A, US-A-3876391, US3876391 A, US3876391A|
|Inventors||George W Eckert, Frederic C Mccoy|
|Original Assignee||Texaco Inc|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (6), Referenced by (87), Classifications (25)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 1191 McCoy et a1. 1 Apr. 8, 1975  PROCESS OF PREPARING NOVEL MICRO 1.989.528 1/1935 Rather et a1. 44/72 EMULSIONS 2.021.088 12/1935 2.111.100 3/1938 Kokatnur 44/51  Inventors: Frederic C- M C y. B ac n: George 3.458.294 7/1969 Nixon et a1. 44 51 W. Eckert, Wappingers Falls. both 3.527.581 9/1970 Brownuwell et a1. 44/51 of NY.
1 1 Asslgneel TeXaco. New YOfk- Primary E.\'aminerD an1el E. Wyman 22 F1 d: A 29 I97] Assist/m! E.\'aminer-Y. H. Smith l l 0 ug Attorney. Agent. or FirmThomas H. Whaley; Carl G. [211 Appl. No.: 174,546 Ri Related U.S. Application Data  Continuation-impart of Ser. No. 803.459. Febv 28.
1969. abandoned. 1 1 ABSTRACT 1521 vs. c1 44/51; 252/309 This invention concerns a Process for Preparing 51 Im. 01 c101 1/32 in'petwleum of emulsions-  Field of Search 44/5 7] 252/308 sions are stable and clear and contain substantially greater quantiticsof water-soluble additives than it is normally possible to disperse when using the petro-  References Cited lcum fraction alone.
UNITED STATES PATENTS 10 Claims No Drawings 1.789.302 1/1931 Calcott et :11. 44/71 PROCESS OF PREPARING NOVEL MICRO EMULSIONS This application is a continuation-in-part of Ser. No. 803,459 filed Feb. 28, 1969 now abandoned in the United States Patent Office.
This invention relates to a process for increasing the quantity of water soluble additives that can be incorporated into petroleum fractions and to the emulsions produced therein.
More particularly, this invention concerns a process for preparing stable, clear micro emulsions of petroleum fractions and water containing substantially greater quantities of water-soluble additives than is possible using the hydrocarbon fractions alone.
The use of additives in petroleum fractions derived from petroleum refining is well established in the industry. Additives are commonly utilized to enhance, improve, modify, suppress or change some property or characteristic of the hydrocarbon fraction treated. For example, lubricating oils contain viscosity index improvers, pour point depressants, oxidation and corrosion inhibitors, while furnace and residual fuel oils employ stabilizers, corrosion inhibitors and the like. Middle distillates, such as diesel fuels and jet fuels particularly, utilize a variety of additives to improve performance. These include ignition improvers, cetane improvers, corrosion inhibitors, deicers among others. Many additives, including octane number improvers, gum inhibitors, metal deactivators and rust preventives are commonly employed in gasolines.
One of the limiting factors in the use of many potentially attractive additives is their poor solubility in the neat petroleum fraction to be treated. For example, a good number of amides, diols, alkanolamines, polyamines and aldehydes which have good solubility in water are insufficiently soluble in petroleum fractions to impart any significant additive effect. As used herein, good solubility in water is defined as permitting a clear solution containing at least a percent by weight of the additive in water to be prepared which is stable at C. lnsufficiently soluble in a petroleum fraction is defined as not permitting a clear 0.1 percent by weight solution of the additive to be prepared which is stable at 25 C. (77 F.) in petroleum fractions covering a range of volatility from an Initial Boiling Point (IBP) of about 70 F. (21 C.) to an End Point (EP) of about 650 F. (343 C.) as determined using ASTM Method D-86. Y
The use of micro-emulsions of petroleum fractions in water is old in the art per se. These emulsions have been used in order to increase the quantity of certain additives in said petroleum fractions. Unfortunately, the results have been generally unsatisfactory particularly where the emulsions end use is in motor fuel compositions. One problem has been the unattractive,
milky or opaque appearance of the emulsions. A more important failing has been the instability of the emulsion. For example, even the best emulsion eventually separates into two phases under stress and even under ideal storage conditions, some separation occurs within a relatively short time. The breaking of the emulsion is undesirable since it then becomes impossible to deliver homogenous fuel samples into the carburetor. Another problem of the prior art covering fuel-water emulsions has been that/the surfactants are inherently corrosive to metals or have contained ash-forming metals. Furthermore, preparation of the emulsions of the prior art has required the use of high speed, high shear devices such as colloid mills and homogenizers.
Recently the inventors have developed a novel process of preparing stable, transparent water-in-oil emulsions, capable of dispersing substantially greater quantities of many water-soluble additives than can be dispersed in the neat petroleum fraction alone. Not only does the process enable the preparation of additiverich dispersions but, in addition, the dispersions have viscosities similar to those of the petroleum fraction and thus, in the case of gasolines, they are readily carburetted. Also, they are perfectly clear to the eye for extended periods of time and utilize non-corrosive and ashless surfactants. In addition, the dispersions can be made using only moderate agitation such as is provided by conventional fuel blending equipment. This unique combination of properties was heretofore unobtainable and represents a significant advance in the art.
It is therefore an object of this invention, among others, to provide a novel process for preparing stable, clear, low-viscosity dispersions of petroleum fractions (such as gasoline or middle distillates) with water containing much greater quantities of water-soluble additives than has previously been possible.
It is a further object of this invention to provide stable, transparent, additive-rich water-in-oil emulsions which can be used as concentrates to incorporate substantial quantities of additives into petroleum fractions in which the additives are normally insufficiently soluble.
A specific object of this invention is the preparation of stable and clear gasoline compositions modified by the addition of water-soluble additives, said gasoline having increased octane numbers compared to the unmodified base fuel.
Additional objects will suggest themselves to those skilled in the art after a further reading of this application.
In practice, the above objects are achieved by a process wherein micro-emulsions comprising petroleum fractions and water are prepared using any of the procedures described below.
In one procedure an aqueous solution of the one or more water-soluble additives to be dispersed and an effective amount of at least one water soluble surfactant are added to the petroleum fraction preferably with brisk agitation. Then an effective amount of at least one petroleum fractionsoluble surfactant is incrementally added (titrated) to the agitated two phase system until a clear blend is produced. At this point a stable, clear, micro-emulsion of water-in-petroleum" containing the surfactants, water, petroleum fractions and additives is formed in which the average particle diameter of the dispersed phase is 0.1 micron or smaller. These micro-emulsions can be used to achieve the objects of this invention. This procedure is particularly useful where the quantities of the two different surfactants required are unknown. The following represent alternative procedures.
In one alternative process the petroleum fraction to be emulsified is blended with the required quantities (as determined supra) of at least one petroleumfractionsoluble surfactant and at least one water soluble surfactant until a homogeneous mixture is obtained. Then an aqueous solution of the water-soluble additive or additives to be dispersed is added with agitation until a clear dispersion results. Again, the stability of the resultant microemulsions is as above.
Another alternative process is to prepare two separate blends, one of distillate containing the required amount of petroleum-fraction-soluble surfactant or surfactants, the other of water containing required amount water-soluble additive and water-soluble surfactants. Then the water blend is blended into the distillate blend until a clear micro-emulsion, identical in all its properties to those above, is prepared.
To further aid in the understanding of the invention, the following supplementary disclosure is submitted:
A. PETROLEUM FRACTIONS As used throughout this disclosure, the term refers to fluid products derived from petroleum refining having an Initial Boiling Point range from about 21 C (70 F.) to an End Point of about 343 C. (650 F.) Illustrative fractions include middle distillates (such as gas oils, furnace oils, kerosene, diesel fuels) motor gasolines and aviation gasolines.
B. SURFACTANTS l. HLB VALUE OF SURFACTANT The term HLB value as used herein refers to the hydrophile-lipophile balance of a surfactant. That is, the relative simultaneous attraction that the surfactant demonstrates for water and oil. Substances having a high HLB, above about 12, are highly hydrophilic (and poorly lipophilic) while substances having a low HLB, below about 8, are lipophilic and consequently poorly hydrophilic. Those having an HLB between about 8 and 12 are intermediate. An extensive discussion of HLB can be found in the literature particularly in Emulsions: Theory and Practice, by P. Becher, published by Reinhold Publishing Corp., N.Y., 1957.
2. PETROLEUM-FRACTION-SOLUBLE As used throughout this application, refers to surfactants of the anionic, cationic or nonionic type. They must be both ashless upon ignition and soluble to the extent that at least a clear percent by volume solution and preferably a clear 30 percent by volume solution of the surfactant can be prepared which is stable at 25 C. An additional requirement is that when in the presence of both the petroleum fraction and water they are preferentially soluble in the petroleum fraction.
Illustrative petroleum fraction soluble surfactants include, among many others, the following materials sold under various proprietary means by different manufacturers; aliphatic esters of diethylene glycol such as diethylene glycol monolaurate, the mono and diesters of polyols such as sorbitol mono-palmitate, sorbitol monolaurate, polyoxyalkylated mono-diand poly aliphatic esters of polyols such as mannitol dioleate, sorbitol monostearate, sorbitol monolaurate, as well as certain of the polyoxyalkylated alkylated phenols. In fact, the only limitation other than their solubility in petroleum fractions and freedom from ash-forming components is that the surfactants have hydrophilelipophile balance (HLB) values, as outlined in the preceding section, in the range of about 3-10.
3. WATER-SOLUBLE SURFACTANTS As used throughout this disclosure this term refers to surfactants of the anionic, nonionic or cationic type which must be ashless upon ignition and soluble in water to the extent that at least a clear 10 percent by volume solution and preferably at least a clear 30 percent by volume solution of the surfactant can be prepared which is stable at 25 C. Furthermore, in the presence of both petroleum fraction and water, they are preferentially water-soluble.
Illustrative water-soluble surfactants include, among many others, the following materials sold under various proprietary names by different manufacturers; the fatty acid salts of polyalkanolamines, such as triethanolamine oleate, amine salts such as C tertiary alkyl primaray amine acetate and dodecylamine hydrochloride, quaternary ammonium salts such as soya trimethyl ammonium chloride, alkylated tertiary amine salts such as N-cetyl-N-ethyl morpholinium ethosulfate, as well as certain of the polyoxylated alkylated phenols, polyoxyalkylated alkyl ethers, polyoxyalkylated aliphatic esters of polyols, polyoxyalkylated aliphatic amines, alcohols, acids and amides. More specific illustrations of these polyoxyalkylated materials include nonyl phenol, stearyl, lauryl and oleyl amides, sorbitolmonooleate, sorbitol monolaurate, sorbitol monostearate and sorbitol monopalmitate, as well as stearyl, oleyl and tridecyl alcohols, all polyoxyethylated with from about 850 moles of ethylene oxide.
Again, the only limitation other than water solubility and freedom from ash is that the HLB value, as defined in the preceding section, be in the range of about 10-35.
It should be noted that the sole limitation on the use of the various pairs of surfactants, is that the use of cationic and anionic surfactants in the same dispersion are to be avoided since they usually tend to be incompatible.
C. WATER-SOLUBLE ADDITIVES As indicated earlier, this term refers to various compounds of diverse structure which share in common: (a) that they have sufficiently good solubility in water to enable a clear 10 percent by weight solution of the additive to be prepared which is stable at 25 C; (b) that they are insufficiently soluble in petroleum fractions (such as gasoline and middle distillate fractions) to change, enhance or otherwise favorably modify some property or characteristic of the petroleum fraction such as octane or cetane number, surface ignition properties, smoke formation, exhaust emissions or the like. Gasoline may contain octane improvers, antioxidants, metal deactivators and anti-icing agents among other types of additives.
The favored water-soluble additives which function especially well in this process and which form stable and clear dispersions are those selected from the group consisting of aliphatic diols, aliphatic amides, alkanolamines, polyamines and aliphatic aldehydes.
The additives particularly preferred are certain specific compounds of the group which have been found to increase octane numbers in motor fuels when they comprise from about 1 to 10 percent by volume or higher of the final fuel dispersion. These preferred additives are selected from the group consisting of formamide, acetamide, ethylene glycol, urea, ethylene diamine, propylene diamine, meta-phenyline diamine and formaldehyde.
D. CONCENTRATIONS AND RATIOS OF THE COMPONENTS 1. WATER Ordinarily, the amount of water required to solubilize the water-soluble additive or additives to be used is the most important factor in determining the concentration of the other components. A minimal amount of water is employed depending upon the solubility of the additive in water and the amount of additive required to achieve the desired effect. In most instances the volume of water will make up from 05-30 percent of the final dispersion with the best results being obtained where the water makes up from 5-10 percent of the final dispersion volume.
2. ADDITIVES The total parts by volume of additives employed per 100 parts by volume of micro-emulsion is a variable dependent upon several factors. These include the application for which the additive is employed, the cost of the additive, as well as the maximum amount of additive that can be dispersed in a given micro-emulsion prepared using a particular pair of surfactants. In many instances a range of from 0.1 to parts by volume of additive per 100 parts by volume of the final microemulsion will suffice. More usually, a narrower range of 2 to 7 parts of additive per 100 parts by volume of microemulsion can be employed.
For example, to increase the octane number of gasoline, each 100 parts by volume of the final, clear gasoline composition will comprise:
a. from about 1 to 10 parts by volume additive,
b. from about 6 to 16 parts by volume of water,
c. from about 6 to 16 parts by volume of total surfactant, and
d. from about 87 to 58 parts by volume of the gasoline whose octane number is to be raised.
3. SURFACTANTS The total amount of surfactant pairs required and the ratio of the two types to each other (high I-ILB, abbreviated as H and low HLB, abbreviated as L) depends primarily on the amount of water, the nature of the additives and their concentration in the formulation as are discussed below:
a. Total amount of surfactant Each surfactant may comprise as little as 1 part by volume or as much as 12 parts by volume. This range of quantities is referred to as an effective amount of surfactant.
b. Combined HLB of the surfactant pair This is calculated by the following formula:
(/2 by vol. "H" X HLB ol H") (W by vol. H" '71 by vol, L")
The combined HLB of the surfactant pair may range from about 7 to 20, however, the best results are consistently obtained at 8-12 and for this reason this is preferred.
c. Ratio of HzL surfactants Whatever the intended end use, it is critical that the proper ratio of hydrophilic (water soluble) surfactant to lipophilic (petroleum fractionsoluble) surfactant be used. The H:L ratio is calculated as follows:
0 pletely unsuitable for the applications of this invention.
d. Petroleum fractions these make up the major portion of the total dispersion volume and can comprise from 58 to 87 parts by volume of the dispersion. Ordinarily, from to parts by volume of the final dispersion are present as the petroleum fraction. Included in this category are the hydrocarbons present in conventional motor gasolines, kerosenes, furnace oils, diesel fuels and gas oils.
E. AGITATION Whenever agitation is mentioned in the above procedures it is to be understood that conventional stirring or mixing equipment is satisfactory. In other words, no excessive shearing or high speed blending devices are necessary.
F. PREFERRED COMPOSITIONS While the inventive process is fully operable to the extent disclosed, some more specific aspects of the inventive process produce the best results, and are therefore preferred.
As previously outlined, it has been found that if particular care is taken in the selection of the two types of surfactants, greatly improved results are obtained. For example, more favorable results are obtained when the distillate-soluble surfactant be selected from those having an HLB value from about 3-10 with the best results being when the petroleum fraction soluble surfactant has an HLB dispersion value from about 5-9.
Similarly, when the above-described petroleum fraction-soluble surfactants are used in conjunction with water-soluble surfactants having HLB values from about 1035, superior results are obtained. This is particularly the case where a non-ionic water-soluble surfactant having an HLB value of from about 12-15 is used. If an anionic watersoluble surfactant is used, the preferred I-ILB range is 30-35. Thus the preferred process conditions of this invention are those in which at least one petroleum fraction-soluble surfactant having an HLB value of from 5-9 is used in conjunction with at least one non-ionic water-soluble surfactant whose I-ILB value is from 12-15, with the l-I/L (hydrophilelipophile) ratio calculated as previously described is combined HBL ol'surfuctunt pair about 3:1 or less.
In order to disclose this invention in the greatest possible detail the following illustrative examples are submitted:
Unless specified otherwise, all temperatures are in degrees fahrenheit F.) and all percentages or parts are by volume. In all instances the volatility characteristics such as IBPs and EPs are determined by ASTM EXAMPLE 1 the aqueous urea solution until a homogeneous solution is obtained. To 75 parts by volume of the vigorously stirred solution (containing 5.5 parts by vol. of urea, 49.5 parts by vol. water and 20.0 parts by vol. surfactant) is added 391 parts by volume of base gasoline (whose properties appear below),
Gravity APl 59.3 Reid Vapor Pressure 9.2 lbs.
Distillation FlA Analysis (Fluorescent Indicator Analysis) lBP 71 F. 30.57! Aromatics EP 369 F. 13.0% Olefins 56.5 Saturatcs a second blend is prepared by dissolving 10 parts by weight of urea (7.5 parts by volume) into 70 parts by weight of water (70 parts by volume) and adding to the stirred urea solution parts by weight (20.3 parts by volume) of a water-soluble surfactant (nonylphenol ethoxylated with 9.5 moles of ethylene oxide). After the second blend becomes homogenous, 19.5 parts by volume are blended into the gasoline blend using vigorous agitation. After a short time a clear microemulsion is obtained, identical in all respects to the second emulsion prepared in Procedure A.
Procedure C A blend of the unleaded base gasoline of Procedure A is obtained by stirring 78.0 parts by volume of the gasoline and 4.0 parts by volume of the water soluble ethoxylated nonyl phenol of Procedure A and 6.8 parts by weight of the gasoline-soluble ethoxylated nonyl phenol of Procedure A. until a homogenous mixture is with continued stirring (when stirring is discontinued the mixture separates into 2 phases. A gasoline-soluble surfactant [N-40, a nonyl phenol ethoxylated with an average of4 moles of ethylene oxide (HLB=9)] is then added in increments until a clear, transparent microemulsion is obtained. The total gasoline-soluble surfactant added is 34 parts by volume. The stable, clear, fluid microemulsion contains 1.1 percent by volume of urea whereas less than a 0.1% solution of urea in the neat base gasoline can be obtained using conventional dissolution procedures. The total HLB of the two sur- 3 factants is 11.2 and the H/L ratio is 2.4 to l.
The same procedure is used to incorporate 1.5 percent by volume of urea using 14.1 percent by volume water, 4.1 parts by volume of water-soluble surfactant and 5.4 parts by volume of the gasoline-soluble surfactant. The HLB of the surfactants is 10.1 and the H/L ratio is 0.9 to 1.
Procedure B A 5.6 parts by volume portion of the gasoline-soluble surfactant of Procedure A (nonylphenol ethoxylated with 4 moles of ethylene oxide) is blended into 74.9 parts by volume of the unleaded base gasoline of Procedure A until a homogenous solution is obtained. Then obtained. To the stirred mixture is slowly added 11.2
20 parts by volume of a 13.8 percent by weight (10.7 percent by volume) aqueous urea solution previously prepared. After the addition is complete a clear, microemulsion results. This is identical to the corresponding microemulsions prepared in Procedures A and B.
EXAMPLES 2-9 Preparation of micro-emulsions containing additional water-soluble additives.
In these examples Procedure A of Example 1 is used to formulate the micro-emulsions. The unleaded gasoline of Example 1 is used as the petroleum fraction. Three-surfactants designated N-40, N- and N are employed. N-40 is a nonylphenol ethoxylated with 4 moles of ethylene oxide and is a gasoline soluble surfactant. N-60 is nonylphenol ethoxylated with 6 moles of ethylene oxide and is also a gasoline soluble surfactant, while N-95 is nonylphenol ethoxylated with an average of 9.5 moles of ethylene oxide and is a watersoluble surfactant. The concentrations of the water, gasoline, surfactant and additive components are shown in Table l, which also lists the additives and surfactants used and the data from Example 1.
The figure in parenthesis following each surfactant is the proportion of the total HLB contributed by each surfactant. For example, in Table 1, Example 1, N-95 contributed 7.9 and N40 contributed 3.3 for a total HLB of 1 1.2. The 1-1:L ratio in this case is 7.9/3.3 2.4 to 1.
TABLE 1 PREPARATION OF MlCROEMULSlONS Concentration (parts b\' volume) of Components of Emulsion Petroleum Com- Formu- Water-Soluble Atltli- Water-Soluble Petroleum Fraction Fraction hined Hzl. lation Ex. Atlditiw ti\c Surfactant Soluble Surfactant Water l HLB Ratio Procedure 1 Urea 1.2 6.9 N-95 (7.9) 4.0 N-40 (3.3) 77.9 11.2 2.411 A.B.C
1.5 3.8 N-95 (4.7) 5.7 N-40 (5.4) 14.2 74.8 10.1 0.911 A 2 Ethylene Glycol 2.0 5.8 N-95 (6.8) 4.9 N-40 (4.1) 10.0 78.3 10.9 1.7:1 A 5.0 5.0 N-95 (7.9) 3.0 1\'-40(3.4) 10.0 77.0 11.3 2.411 A 5.0 5.0 N-95 (7.9) 2.9 1\'-40 (3.3) 15.0 72.1 11.2 2.4:1 A 3 Formamltlc' 1.0 4.2 N 95 (5.0) 5.4 N-40 (4.6) 10.0 78.4 10.6 0.0:1 A
1.0 N-60 (1.0) 2.0 4.2 N-95 (5.4) 5.5 N-40 (5.1) 10.0 78.3 10.5 1.111 A 5.0 2.5 N-95 (4.7) 4.1 N-40 (5.7) 10.0 78.4 10.4 0.8:1 A 4 Acetamide 4.4 4.2 N-95 (5.1) 6.0 N-40 (5.3) 10.0 75.4 10.4 1:1 A 5 Ethano1aminc(mono) 2.0 5.0 N-95 (7.0) 40 N40 (4.0) 100 79.0 11.0 1.8:1 A 5.0 6.5 N-95 (9.2) 2.3 N-40 (2.4) 9.9 76.4 11.6 3.821 A 6 Ethylene Diamine 2.5 5.5 N-95 (8.5) 2.6 N-40 (3.1) 10.5 78.9 11.6 2.7:1 A 7 Propane Diamine 5.0 8.5 N-95 (9.9) 1.6 N-40 1.3) 10.0 74.3 1 1.8 5.2:1 A
0.6 N-60 (0.6) 8 m-Phenylene Diamine 1.0 4.2 N-95 (5.3) 5.0 N-40 (4.9) 9.9 79.9 10. 1.1:1 A 9 Formaldehyde 4.2 3.0 N-95 (4.2) 6.0 N-40 (6.0) 6.8 80.0 10. 0.7:1 A 5.7 4.4 N9 (60) 4.8 .\'-40 (4.7) 15.2 69.9 10.7 1.311 A "'(iasoline in Examples l-9 EXAMPLES 10-14 Petroleum Fraction lBP EP Preparation of micro-emulsions of gasoline and water No. 1 Furnace Oil 350 525 containing ethylene glycol using other surfactant pairs. Egii 253 In these examples micro-emulsions of gasoline and water containing ethylene glycol are prepared using Procedure A of Example 1; Table 2 shows the concen- EXAMPLES 7 and 18 to 25 trations of the micro-emulsion components as well as Establishing criticallty of ratio the total HLB, the individual HLB and the H:L ratio of The compositions in these examples, shown in Table the surfactant pairs used. All of the blends are clear flu- O Cover ratios from to 1 to to ids f low viscosity clude five different water-soluble additives, four different additive pairs and two petroleum fractions. It will be seen that at an H:L ratio of 7: 1, the clear, fluid com- EXAMPLES 1516 positions of the present invention were not obtained, while at ratios of from 0.8 to l to 5.2 to l the desired The preparation of micro emulsions using other petrofluid, clear microemulsions were obtained. Thus it is leum fractions. evident that an H:L ratio of less than about 7 is critical Using the blending technique of Procedure A, microto the formation of the compositions of this invention. emulsions are prepared using No. 2 Diesel Fuel and The emulsions were judged by appearance while the Kerosene as the petroleum fraction, ethylene glycol as type (water in petroleum or petroleum-in-water) of the additive and ethoxylated nonylphenols as the sur- 2O emulsion was determined by electrical c0nductance* factant pairs. In all instances clear and stable microto see if the desired satisfactory water in petroleum emulsions are produced. Compositions are shown in fraction type was obtained. As shown in Table 3, satis- Table 2. factory water-in-petroleum emulsions can only be TABLE 2 PREPARATION OF MICROEMLLSIONS USlNG \'AR1OL.'S SURFACTANT PAIRS Concentration (parts by volume) of Components of Emulsion Petroleum (ont- Pro- Water-Soluhlc Addi- Water-Soluble Petroleum Fraction Fraction bined H:L cc- Additi e ti e Surfactant Soluble Surfactant Water l HLB Ratio dare 10 Ethylene (.ilycol .0 4.2 NH Lauryl Sulfatc( 12.7) 6.0 N-40 (5.3) 10.8 74.0 18.0 2.411 A l l Ethylene Glycol 5.0 2.0 Triethanolamine Lauryl Sulfate (6.8) 10.0 N-40 (7.2) 10.0 73.0 14.0 0.911 A 12 Ethylene Glycol 5.0 5.0 C t-A|kylprimary Amine Aeetate 0.0 N40 10.0 74.0 A 13 Ethylene Glycol 5.0 3.0 Ethanolamine Octyl Orthophosphatc 9.0 N40 12.0 71.0 A 14 Ethylene (ilycol 5.0 6.0 Tween 40 (8.5) 5.0 SPAN 20(3.9) 10.0 74.0 12.4 2.211 A 15 Ethylene Glycol 5.0 5.0 N-95 (5.7) 6.0 N-40 (4.9) 10.0 74.0 10.6 1.121 A 16 Ethylene (ilycol 5.0 4.8 N95 (5.7) 5.6 N-40 (4.9) 10.0 74.6 10.6 1.1:1 A
(lllliescl l'ucl (ll1l-375l-; EP-600F) used in Example 14. Kerosene (ll3P-330F: EP-5l5l-) used in livnnple 15. All others used (iasoline. Since the H1. of one of the surfactants i not kmmn. the combined HLB and H11. ratio are not shown.
achieved when the combined HLB is below about 12 and the H to L" ratio is at least 0.8:1 to 52:1, preferably from 1:1 to about 4: 1.
* The electrical conductance method involves inserting two electrodes in series with a battery and a galvanometer into the emulsion. In case of an O/W emulsion, there is a deflection of the galvanometer because of the conductivity of the continuous (aqueous) phase. In the W/O type of emulsion no deflection is observed since the continuous (oil) phase is non-conducting.
TABLE 3 EXAMPLES SHOWING CRl'l'lCALlTY OF H/L RATIO Concentration (parts by volume) of Components of Emulsion Water-Soluble Water-Soluble Petroleum Fraction Petroleum Ex. Atldithc Additive Surfactant Soluble Surfactant Water Fraction 3 Formamide 5.0 2.5 N-95 (4.7) 4.1 N-40 (5.7) 10 78.4 Gasoline 1 Urea 1.5 3.8 N-95 (4.7) 5.7 N-40 (5.4) 14.2 74.8 Gasoline 18 Ethylene Glycol 2.0 6.0 N95 (5.8) 7.0 N- (3.2) 10.0 75.0 .lP-4 19 Ethylcne Glycol 2.0 6.0 N-95 (6.3) 6.0 SPAN 80 (2.2) 10.0 76.0 .lP-4 20 Ethylene Glycol 2.0 5.0 Tween 80 (7.5) 5.0 SPAN 80 (2.2) 10.0 78.0 .IP-4
5 Ethanolamine(- 2.0 6.4 N95 (9.2) 2.3 N- (2.4) 9.9 76.4 Gasoline mono) 7 Propane Diamine .0 8.5 N-95 (9.9) 1.6 N-40 1.3) 10.0 74.3 Gasoline 0.6 N- (0.6) 17 Ethylene Glycol 2.0 6.0 N-95 (10.4) 1.2 N-40 (1.5) 10.0 80.8 JP 4 21 Fori'namidc 1.14 1.44 Tween (10.8) 0.56 PAN 80 (1.2) 0.86 96.0 .lP-4
TABLE 3 Continued 7 1-\.\.\l11.l-S SHOWING(R111('.-\l.|'1\'()l- H 1. RAllt) Concentration lpal'ts by \olumel ol' ('omponems o1 l'nullsion ater-Soluhltalter-Soluble Petroleum l'raution Petroleum l-\ Additnt- Additiw Surfactant Soluble Surfactant aler l'raction 22 Formamide 1.1-1 1.62 Tween 80 1 12.1 0.38 SPAN 80 (0.81 0.86 96.0 JP-4 "3 Ethylene (ily-col 2.5 4.0 Tween 80 12.1) 1.0 SPAN 80 (0.8) 2.5 90.0 JP-4 24 Ethylene (ilycol 2,0 8.0 Tween 80 12.0) 2.0 SPAN 80 (0.8) 40.0 78.0.1P-4 25 Ethylene Glycol 1.0 1.36 Tween 801 13.651 0.14 SPAN 80 (0.36) 1.0 96.0 JP-4 Combined Emulsion Emulsion Yield Stress Mixing Ex. HLB Hzl. Ratio Type Appearance Dyms/cm Procedure 3 10.4 0.8:1 \v/o Clear liquid 1 1) I 10.1 0.9:] \\'/o (lcar liquid 0 (1) 18 9.0 1.811 \\/0 Clear liquid 0 (l) 19 8.4 2.9:1 \v/o Clear liquid 0 (1) 20 9.7 3.511 \v/o Clear liquid 0 (1) 1 1.6 3.811 \\/n Clear liquid 0 (l) 7 11.8 5.2:1 \v/o Clear liquid 0 (I) 17 I 1.9 7:1 o/\v Gel 2000 (2) 21 12.0 9:1 o/\\' (iel 1900 (2) 22 12.9 :1 o/\v Gel 3550 (2) 23 12.9 15:1 o/w Gel 850 (21 24 12.8 15:1 o/\\' G01 2000 (2) 25 14.0 38:1 o/\\' Gel 1200 (2) l 1 1 Mieroemulsion formed with eomentional stirring. I11 (iel forms using mixing procedure o1 Nixon. el al. Otherwise. no emulsion.
EXAMPLES 26-34 Engine tests on the gasoline-in-petroleum microemulsions of Examples 1-9.
Comparisons were made in terms of octane number between the transparent motor fuel compositions (microemulsions) of Examples 1 to 9 and the unleaded base fuel used as the gasoline stock in Examples 1 to 9. A Research ASTM D-908-47T (CFR Engine) Method was used and the testing procedure of ASTM Operating Conditions was 600 rpm and 125 F. intake air temperature. The engine operated unthrottled with carburetted fuel supply. Controlled operating parameters were speed, intake air temperature, intake air humidity, compression ratio, mixture strength and spark timing. Table 4 summarizes the data.
As can be seen from Table 4, increases in octane numbers ranging from 1.7 to 9.6 units can be obtained As the preceding specification has demonstrated, several advantages accrue from the practice of this invention, both in the process and product aspects.
For example, the inventive process provides a simple, reproducible method of increasing the quantity of normally poorly soluble additives that can be incorporated into gasolines and middle distillates such as diesel fuels, automotive fuels and aviation fuels. In a more specific vein, the process of this invention provides an alternative means of upgrading the cetane or octane numbers of the above distillates using readily available, and easily handled additives. It also provides a means of incorporating water in fuels in an extremely stable form without the necessity of using any equipment other than conventional blending devices.
In its product aspect this invention provides stable and clear micro-emulsions of distillate fractions and water which incorporate greater quantities of additives over base fuel containing the same quantities of water. than has been heretofore possible to solubilize in the Table 4 Engine Tests on Emulsions from Examples 1 to 9 "/1 by Vol. '/r by Vol. '71 by Vol. Ex. Formulation Water-Soluble Additive in Water in of Total Research Octane 1 Additive Formulation Formulation Surfactants Octane Number Increase Base Fuel None 93.3 Base Fuel None 10 9.6 94.7 1.4 Base Fuel None 15 10.5 96.3 3.0 26 Example 1 Urea 1.2 10.0 10.8 96.0 1.3 1.5 14.0 9.5 99.1 2.8 27 Example 2 Ethylene glycol 2.0 10.0 10.7 98.0 3.3 5.0 10.0 8.0 98.8 4.1 5.0 15.0 7.9 103.0 6.7 28 Example 3 Formamidc 1.0 10.0 10.6 96.1 1.4 20 10.0 9.7 101.8 7.1 5.0 10.0 6.6 101.6 6.9 29 Example 4 Acctamide 4.4 10.0 10.2 97.4 27 30 Example 5 Ethanolamine 2.0 10.0 9.0 97.9 3.2 5.0 9.9 8.7 98.9 4.2 31 Example 6 Ethylenediamine 2.5 10.5 8.1 104.3 9.6 32 Example 7 Propanediamine 5.0 10.0 10.7 99.2 4.5 33 Example 8 m-phenylene-diamine 1.0 9.9 9.2 98.5 3.8 34 Example 9 Formaldehyde 4.2 6.8 9.0 96.5 1.8 5.7 15.2 9.2 99.6 3.3
11 1 Oclane increase abou: l'uel le\el \\ithout water-soluble additive.
neat distillate. In its more specific product embodiment this invention provides gasoline-additive compositions that have substantially improved octane numbers compared to the untreated gasolines.
This invention is also advantageous over the closest known art. U.S. Pat. No. 3,458,294 (Nixon et al.) who discloses processes of preparing emulsions of gliquid hydrocarbon containing major amounts of liquid hydrocarbon and as a continuous phase a minor portion of polar organic liquid including minor amounts of additives. Some salient differences between the claimed invention and Nixon et al. are:
a. The applicants always utilize water, Nixon may or may not.
b. We require at least two surfactants, Nixon may use one.
c. Applicants compositions are water-in-petroleum fraction type emulsions while the patentees are petroleum fraction-in-water type emulsions.
d. Our compositions have viscosities close to that of the petroleum fraction phase (zero yield value). Nixons are grease-like compositions having yield stresses of from 850 dynes/cm (see composition b, Table VII) to 3550 dynes (composition C, Table VI).
e. Our blending process is essentially independent of the order of addinv the components or the type of mixing employed. In contrast, unless the order of addition and type of mixing, both disclosed in Nixon, are used, the desired type of product is not obtained.
f. Finally, in applicants claimed process, unless the critical ratio of hydrophilic surfactant to lipophilic surfactant (less than 6: l preferably from about 3:1 to 0.8:1) is utilized, the desired results are not obtained. That is, above 6:1 leads to the formation of either very viscous, gel-like emulsions or no emulsions, depending on the mixing technique.
Finally, this invention is advantageous in that numerous modifications, substitutions and changes can be made in both its process and product aspects without departing from the inventive concept. The metes and bounds of this invention are best determined by the claims which follow, read in conjunction with the specification.
What is claimed is:
1. A stable, clear motor gasoline composition having substantially higher octane numbers than unmodified base fuels consisting essentially of an admixture of the following components in the proportions indicated:
a. from about 58 to 87 parts by volume of gasoline,
b. from about 6 to 16 parts by volume of water,
c. from about 3 to 8 parts by volume of at least one gasoline-soluble surfactant having an HLB value from about 5 to 9, said surfactants selected from the group consisting of diethylene glycol monolaurate, sorbitol monopalmitate, sorbitol monolaurate, polyoxyalkylated mannitoldiolate, polyoxyalkylated sorbitrol monostearate, polyoxyalkylated sorbitol monolaurate and polyoxyalkylated alkylated phenols,
d. from about 3 to 8 parts by volume of at least one water-soluble surfactant having an HLB value from about 10 to 35, selected from the group consisting of C tertiary alkyl primary amine acetate, dodecylamine hydrochloride, ammonium lauryl sulfate, triethanolamine sulfate, ethanolamine octyl ortho phosphate, polyoxyalkylated nonyl phenol, polyoxyalkylated stearyl amides, polyoxyalkylated lauryl amides, polyoxyalkylated oleyl amides, polyoxyalkylated sorbitolmonooleate, polyoxyalkylated sorbitol monolaurate, polyoxyalkylated sorbitol monostearate, polyoxylated sorbitol monopalmitate, polyoxyethylated stearyl alcohol, polyoxyethylated oleyl alcohol and polyoxyethylatedtridecyl alcohol,
e. from about 0.5 to 10 parts by volume of a watersoluble, insufficiently gasoline-soluble, additive selected from the group consisting of acetamide, formamide, monoethanolamine, ethylene diamine, propane diamine, and m-phenylene diamine, said parts by volume ratio of water-soluble surfactant petroleum fraction-soluble surfactant do not exceed about 5:1.
2. The fuel composition of claim 1 wherein the additive is ethylene glycol.
3. The fuel composition of claim 1 wherein the additive is formamide.
4. The fuel composition of claim 1 wherein the additive is ethanolamine.
5. The fuel composition of claim 1 wherein the additive is ethylene diamine.
6. The fuel composition of claim 1 wherein the additive is urea.
7. The fuel composition of claim 1 wherein the additive is acetamide.
8. The fuel composition of claim 1 wherein the additive is propane diamine.
9. The fuel composition of claim 1 wherein the additive is m-phenylene diamine.
10. The fuel composition of claim 1 wherein the additive is formaldehyde.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US1789302 *||23 Aug 1929||20 Jan 1931||Du Pont||Gum inhibitor for hydrocarbons|
|US1989528 *||26 Jun 1930||29 Jan 1935||Socony Vacuum Oil Co Inc||Distillate petroleum product and method of treating the same|
|US2021088 *||29 Sep 1932||12 Nov 1935||Texas Co||Motor fuel|
|US2111100 *||26 Aug 1935||15 Mar 1938||Autoxygen Inc||Motor fuels and the methods of making them|
|US3458294 *||16 Mar 1967||29 Jul 1969||Exxon Research Engineering Co||Viscous emulsion of liquid hydrocarbon|
|US3527581 *||17 Oct 1966||8 Sep 1970||Exxon Research Engineering Co||Microemulsions of water in hydrocarbon fuel for engines|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4046519 *||31 Oct 1975||6 Sep 1977||Mobil Oil Corporation||Novel microemulsions|
|US4297107 *||30 Nov 1979||27 Oct 1981||Bayer Aktiengesellschaft||Fuels and their use|
|US4394131 *||14 Mar 1980||19 Jul 1983||Entoleter, Inc.||Combustion fuel emulsion|
|US4395266 *||19 May 1980||26 Jul 1983||Internationale Octrooi Maatschappij "Octropa" B.V.||Stabilized water-in-mineral oil emulsion|
|US4396400 *||14 Apr 1981||2 Aug 1983||Societe Elf France||Process for improving the combustion of gas oils|
|US4410334 *||30 Oct 1981||18 Oct 1983||Parkinson Harold B||Hydrocarbon fuel composition|
|US4451265 *||21 Apr 1981||29 May 1984||The United States Of America As Represented By The Secretary Of Agriculture||Diesel fuel-aqueous alcohol microemulsions|
|US4465494 *||10 Feb 1982||14 Aug 1984||Societe Nationale Elf Aquitaine||Microemulsion of water in a liquid fuel|
|US4477258 *||30 Oct 1980||16 Oct 1984||Labofina, S.A.||Diesel fuel compositions and process for their production|
|US4512774 *||27 Dec 1978||23 Apr 1985||Calgon Corporation||Residual fuel oil conditioners containing metal salts in aqueous solution|
|US4561861 *||1 Nov 1984||31 Dec 1985||Texaco Inc.||Motor fuel composition|
|US4599088 *||30 Aug 1984||8 Jul 1986||Texaco Inc.||Clear stable gasoline-alcohol-water motor fuel composition|
|US4608057 *||3 Jun 1985||26 Aug 1986||Texaco Inc.||Clear stable motor fuel composition|
|US4618348 *||2 Nov 1983||21 Oct 1986||Petroleum Fermentations N.V.||Combustion of viscous hydrocarbons|
|US4666457 *||15 Oct 1985||19 May 1987||Petroleum Fermentations N.V.||Method for reducing emissions utilizing pre-atomized fuels|
|US4684372 *||24 Sep 1984||4 Aug 1987||Petroleum Fermentations N.V.||Combustion of viscous hydrocarbons|
|US4793826 *||27 Sep 1985||27 Dec 1988||Petroleum Fermentations N.V.||Bioemulsifier-stabilized hydrocarbosols|
|US4795478 *||11 Sep 1987||3 Jan 1989||Intevep, S.A.||Viscous hydrocarbon-in-water emulsions|
|US4801304 *||17 Jun 1986||31 Jan 1989||Intevep, S.A.||Process for the production and burning of a natural-emulsified liquid fuel|
|US4834775 *||17 Feb 1987||30 May 1989||Intevep, S.A.||Process for controlling sulfur-oxide formation and emissions when burning a combustible fuel formed as a hydrocarbon in water emulsion|
|US4886519 *||23 Apr 1987||12 Dec 1989||Petroleum Fermentations N.V.||Method for reducing sox emissions during the combustion of sulfur-containing combustible compositions|
|US4976745 *||24 Apr 1989||11 Dec 1990||Domingo Rodriguez||Process for stabilizing a hydrocarbon in water emulsion and resulting emulsion product|
|US4994090 *||5 Mar 1990||19 Feb 1991||Intevep, S.A.||Process for controlling sulfur-oxide formation and emissions when burning a combustible fuel formed as a hydrocarbon in water emulsion|
|US5204022 *||11 Aug 1989||20 Apr 1993||Eastman Kodak Company||Solid-form additive systems dispersible in aqueous media|
|US5259851 *||1 Feb 1991||9 Nov 1993||Eniricerche S.P.A.||Hybrid liquid fuel composition in aqueous microemulsion form|
|US5404841 *||30 Aug 1993||11 Apr 1995||Valentine; James M.||Reduction of nitrogen oxides emissions from diesel engines|
|US5535708 *||29 Aug 1994||16 Jul 1996||Platinum Plus, Inc.||Reduction of nitrogen oxides emissions from diesel engines|
|US5746783 *||8 Nov 1995||5 May 1998||Martin Marietta Energy Systems, Inc.||Low emissions diesel fuel|
|US5809774 *||19 Nov 1996||22 Sep 1998||Clean Diesel Technologies, Inc.||System for fueling and feeding chemicals to internal combustion engines for NOx reduction|
|US6017369 *||23 Nov 1998||25 Jan 2000||Pure Energy Corporation||Diesel fuel composition|
|US6074445 *||20 Oct 1997||13 Jun 2000||Pure Energy Corporation||Polymeric fuel additive and method of making the same, and fuel containing the additive|
|US6183524||11 Apr 2000||6 Feb 2001||Pure Energy Corporation||Polymeric fuel additive and method of making the same, and fuel containing the additive|
|US6190427||11 Apr 2000||20 Feb 2001||Pure Energy Corporation||Diesel fuel composition|
|US6306184||26 Jan 2001||23 Oct 2001||Pure Energy Corporation||Diesel fuel composition|
|US6368366||7 Jul 1999||9 Apr 2002||The Lubrizol Corporation||Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition|
|US6368367||7 Sep 1999||9 Apr 2002||The Lubrizol Corporation||Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel composition|
|US6383237||14 Jan 2000||7 May 2002||Deborah A. Langer||Process and apparatus for making aqueous hydrocarbon fuel compositions, and aqueous hydrocarbon fuel compositions|
|US6419714||16 Jan 2001||16 Jul 2002||The Lubrizol Corporation||Emulsifier for an acqueous hydrocarbon fuel|
|US6530964||6 Dec 2000||11 Mar 2003||The Lubrizol Corporation||Continuous process for making an aqueous hydrocarbon fuel|
|US6652607||6 Dec 2000||25 Nov 2003||The Lubrizol Corporation||Concentrated emulsion for making an aqueous hydrocarbon fuel|
|US6677388||20 Jul 2001||13 Jan 2004||Exxonmobil Research And Engineering Company||Wax transport composition|
|US6827749||15 Oct 2001||7 Dec 2004||The Lubrizol Corporation||Continuous process for making an aqueous hydrocarbon fuel emulsions|
|US6913630||26 Jun 2001||5 Jul 2005||The Lubrizol Corporation||Amino alkylphenol emulsifiers for an aqueous hydrocarbon fuel|
|US6997964 *||13 Nov 2000||14 Feb 2006||Ernesto Marelli||Diesel engine fuel in microemulsion form and method for preparing it|
|US7279017||21 Feb 2003||9 Oct 2007||Colt Engineering Corporation||Method for converting heavy oil residuum to a useful fuel|
|US7341102||28 Apr 2005||11 Mar 2008||Diamond Qc Technologies Inc.||Flue gas injection for heavy oil recovery|
|US7413583||22 Aug 2003||19 Aug 2008||The Lubrizol Corporation||Emulsified fuels and engine oil synergy|
|US7770640||6 Feb 2007||10 Aug 2010||Diamond Qc Technologies Inc.||Carbon dioxide enriched flue gas injection for hydrocarbon recovery|
|US8044232||24 Nov 2006||25 Oct 2011||Akzo Nobel N.V.||Surface-active polymer and its use in a water-in-oil emulsion|
|US8247359||18 Jan 2007||21 Aug 2012||Palox Limited||Water-in-oil emulsions, methods and uses of emulsifying agents|
|US8875666||5 Oct 2010||4 Nov 2014||Universitaet Zu Koeln||Method for the in situ production of fuel/water mixtures in combustion engines|
|US20040093789 *||18 Dec 2001||20 May 2004||Hart Paul R.||Stabilizer blends for alcohol in hydrocarbon fuel|
|US20040111955 *||13 Dec 2002||17 Jun 2004||Mullay John J.||Emulsified water blended fuels produced by using a low energy process and novel surfuctant|
|US20040111956 *||21 Nov 2003||17 Jun 2004||Westfall David L.||Continuous process for making an aqueous hydrocarbon fuel emulsion|
|US20050039381 *||22 Aug 2003||24 Feb 2005||Langer Deborah A.||Emulsified fuels and engine oil synergy|
|US20050049316 *||20 Sep 2004||3 Mar 2005||Burrington James D.||Emulsified water fuel blend containing an aqueous organic ammonium salt|
|US20050183324 *||17 Feb 2005||25 Aug 2005||Ernesto Marelli||Fuel for diesel engines in microemulsion form and method for preparing the same|
|US20060162237 *||19 Jan 2006||27 Jul 2006||Mullay John J||Fuel composition having a fuel, water, a high molecular weight emulsifier, and a surfactant including natural fats, non-ionic and ionic surfactants, co-surfactants, fatty acids and their amine salts, or combinations thereof|
|US20060243448 *||28 Apr 2005||2 Nov 2006||Steve Kresnyak||Flue gas injection for heavy oil recovery|
|USRE36983 *||23 May 1995||12 Dec 2000||Petroferm Inc.||Pre-atomized fuels and process for producing same|
|DE2633462A1 *||26 Jul 1976||23 Mar 1978||Henkel Kgaa||Motor fuels and fuel oils - contg. water and nonionic emulsifier combination, opt. with lower alcohol cpds.|
|DE102009048223A1||5 Oct 2009||16 Jun 2011||Fachhochschule Trier||Verfahren zur In-Situ-Herstellung von Treibstoff-Wasser-Gemischen in Verbrennungsmotoren|
|EP0012292A1 *||1 Dec 1979||25 Jun 1980||Bayer Ag||Motor fuels and furnace oils, preparation thereof and their application|
|EP0020449A1 *||22 Apr 1980||7 Jan 1981||THE GOVERNMENT OF THE UNITED STATES OF AMERICA as represented by the Secretary Department of Commerce||Fire-safe hydrocarbon fuels|
|EP0021471A1 *||20 May 1980||7 Jan 1981||Unilever N.V.||A stabilized water-in-mineral oil emulsion and a process for the preparation of said emulsion|
|EP0194365A1 *||11 Mar 1985||17 Sep 1986||Hydroline Australia Pty. Ltd.||Emulsions|
|EP0505070A1 *||10 Mar 1992||23 Sep 1992||Texaco Chemical Company||Motor fuel composition having enhanced water tolerance|
|EP1101815A2 *||10 Nov 2000||23 May 2001||Ernesto Marelli||Diesel engine fuel in microemulsion form and method for preparing it|
|EP1566430A1 *||15 Feb 2005||24 Aug 2005||Ernesto Marelli||Fuel for diesel engines in microemulsion form and method for preparing the same|
|EP2145940A1||15 Jul 2008||20 Jan 2010||Bp Oil International Limited||Use and vehicle|
|EP2343353A2||18 Jan 2007||13 Jul 2011||Palox Limited||Uses of emulsifying agents in non-aqueous fuels and oils|
|WO1979000211A1 *||11 Oct 1978||19 Apr 1979||Entoleter||Combustion fuel emulsion|
|WO1980000449A1 *||14 Aug 1978||20 Mar 1980||E Cottell||Fuels and methods for their production|
|WO1987002376A1 *||14 Oct 1986||23 Apr 1987||Petroferm Inc||Method for reducing emissions utilizing pre-atomized fuels|
|WO1991004310A1 *||20 Sep 1989||4 Apr 1991||Petroferm Inc||Method for reducing sox emissions during the combustion of sulfur-containing combustible compositions|
|WO1992011927A1 *||26 Dec 1991||23 Jul 1992||H2Oil Corp||Apparatus for making concentrated emulsions|
|WO1995006805A1 *||29 Aug 1994||9 Mar 1995||Platinum Plus Inc||The reduction of nitrogen oxides emissions from diesel engines|
|WO1999013029A1 *||11 Sep 1998||18 Mar 1999||Exxon Research Engineering Co||Water emulsions of fischer-tropsch waxes|
|WO2000053699A1 *||6 Mar 2000||14 Sep 2000||Abu Jawdeh Pauline||Compositions for preparing water-in-oil microemulsions|
|WO2001036570A1 *||17 Nov 1999||25 May 2001||Andras Bertha||FUEL OILS PROVIDING EXHAUST GASES WITH LOW NOx CONTENTS WHEN COMBUSTED|
|WO2004055137A1 *||4 Dec 2003||1 Jul 2004||Lubrizol Corp||Emulsified water blended fuels produced by using a low energy process and novel surfactant|
|WO2008110688A2 *||31 Jan 2008||18 Sep 2008||Biothermie||Method for preparing a biofuel, biofuel thus prepared, and heat production system using such a biofuel|
|WO2011015844A1||23 Jul 2010||10 Feb 2011||Palox Offshore S.A.L.||Composition for preparing an emulsion|
|WO2011042432A1||5 Oct 2010||14 Apr 2011||Universität Zu Köln||Method for the in situ production of fuel/water mixtures in combustion engines|
|WO2011045334A1||13 Oct 2010||21 Apr 2011||Palox Offshore S.A.L.||Protection of liquid fuels|
|WO2011095825A1||7 Feb 2011||11 Aug 2011||Palox Limited||Protection of liquid fuels|
|WO2012158151A1||13 May 2011||22 Nov 2012||H2Oil Corporation||Microemulsion (nanotechnology) additive to oil|
|U.S. Classification||44/301, 516/25, 516/24, 516/26, 516/29, 516/27, 516/30, 516/28|
|International Classification||C10L1/24, C10L1/18, C10L1/26, C10L1/32, C10L1/10, C10L1/12|
|Cooperative Classification||C10L1/191, C10L1/1985, C10L1/328, C10L1/106, C10L1/10, C10L1/2431, C10L1/2658, C10L1/125|
|European Classification||C10L1/10, C10L1/32D, C10L1/10B|