US 3110577 A
Description (OCR text may contain errors)
United States Patent 3,110,577 FUEL OH. COMPGSITIONS Jerome E. Brown, Detroit, Mich, and Hymin Shapiro, East Baton Rouge, and Earl G. De Witt, Baton Rouge, La., assign-ors to Ethyl (Importation, New York, N.Y., a corpoi 'ation of Virginia No Drawing. Filed Apr. 6, 1959, Ser. No. 804,141 3 Claims. (Cl. 494-68) The present invention relates to improved hydrocarbon fuel compositions and more particularly to liquid and semi-solid hydrocarbon fuels for use in heat and light producing apparatus.
Hydrocarbon fuels heavier than gasoline derived from petroleum are utilized in various apparatus such as kerosene lamps, jet type burners, domestic and industrial heating apparatus and the like. They firequently tend to form excessive soot when the burning rate is increased above a certain point which is dependent upon the rate of air flow supplied to the combustion zone, the design of the apparatus and the nature of the specific fuel employed. Thus for any particular combination of variables there is a limit in burning rate beyond which it is impractical to operate in any given system due to the fact that the soot formed deposits on portions of the apparatus and the fact that the. fuel carbonizes instead of completely oxidizing which indicates that the heat or light producing value is not utilized with maximum efficiency.
' 'It is therefore an object of this invention to provide liquid and semi-solid hydrocarbon fuels heavier than gasolines which are capable of higher burning rates with improved efiiciency. A more specific object of this invention is the provision of a liquid hydrocarbon fuel which burns with high effic-iency and a minimum of soot formation. Still further objects will be apparent from the ensuing description.
The above and other objects of this invention are accomplished by providing as new compositions liquid and semi-solid hydrocarbon petroleum distillate and residual fuels heavier than gasoline containing a cyclomatic compound having the general formula MA B wherein M is a metal, namely, nickel; A is a cyclomatic radical, thatis, a cyclopentadienyl radical and B is an elec tron donating group such that a +5x+py=S, wherein S is the atomic number of an inert gas of the fourth period; namely, krypton; x is a small whole integer, namely, 1; y is a small whole integer, namely, 1; n is a perlpd of the periodic table, namely, the fourth period; p is the number of electrons donated by the electron dohating group, namely, 3 and a is the atomic number of the metal, namely, 28/ The amount of such compounds present in the compositions is regulated such that it is equivalent to from 0.001 to about 1 weight percent of nickel.
In other words, the new compositions of this invention comprise a liquid or semi-solid hydrocarbon distillate or residual fuel heavier than gasoline and derived from petroleum containing from about 0.001 to about 1 weight percent of nickel as a cyclopentadienyl nickel nitrosyl compound wherein the cyclopentadienyl radical preferably contains 5 to 13 carbon atoms. As will be seen below, such compositions give rise to a great reduction in soot formation with an increase in burning efficiency.
3,110,577 Patented Nov. 12, lfifiii ice For most applications the beneficial results of the practice of this invention are realized when from 0.002 to about 0.3 weight percent nickel is present in the fuel as a cyclopentadienyl nickel nitrosyl compound. This range of metal concentration is preferred because it may be easily obtained with a minimum of blending control operations, and gives highly satisfactory results.
Reference to the generic [formula described hereinabove indicates that there are three primary constituents in the additive compounds of the present invention. They are the metallic constitutent nickel designated as M, the cyclomatic or cyc'lopentadienyl radical designated as A and an electron donating group, namely, the nitrosyl group, NO, designated as B.
The constituent designated by the symbol A in the formula presented ihereinbefore comprises a cyclomatic radical, that is, a cyclopentadienyl-type hydrocarbon radical which is a radical containing the cyclopentadienyl moiety. In general such cyclomatic hydrocarbon groups can be represented by the formulae Where the Rs are selected from the group consisting of hydrogen and univalent organic hydrocarbon radicals.
A preferred class of cyolomatic radicals suitable in the practice of this invention are those which contain from 5 to about 13 carbon atoms. These are exemplified by cyclopentadienyl, indenyl, methylcyclopentadienyl, propylcyclopentadienyl, diethylcyolopentadienyl, phenylcyclopentadienyl, tert-butylcyclopentad-ienyl, p-ethylphenylcyclopentadienyl, 4- tert-butyl indenyl and the like. The compounds from which these are derived are preferred as they are the more readily available cyclomatic compounds and the metallic cyclomatic coordination compounds obtainable from them have the more desirable characteristics of volatility and solubility which are prerequisites of superior hydrocarbon additives. Moreover, they give the most outstanding results.
The third primary constituent of the new compositions of matter of the present invention is desingated as an electron donating group, namely, the nitrosyl group.
Thus, representative compounds of the present invention include cyclopentadienyl nickel nitrosyl, methylcyclopentadienyl nickel nitrosyl, ethylcyclopentadienyl nickel nitrosyl, propylcyclopentadienyl nickel nitrosyl, indenyl nickel nitrosyl, methyl indenyl nickel nitrosyl, fiuorenyl nickel nitrosyl, dimethylcyclopentadienyl nickel nitrosyl, lnethylpropylcyolopentadienyl nickel nitrosyl, phenylcyclopentadienyl nickel nitrosyl, and the like.
Still another preferred class of compounds falling within the scope of the instant invention are compounds having the formula MA B as defined above, which are liquids at ordinary temperatures. When compounds of the above formula, which are liquids, are employed as additives, they have the important advantages of being readily handled and easily blended with liquid hydrocarbons. Outstanding examples of this class of compound are cyclopentadienyl nickel nitrosyl and methylcyclopentadienyl nickel nitrosyl.
One method for preparing the additives of this invention comprises first forming a dicyclopentadienyl nickel compound by introducing into a compound of nickel a cyclornatic group or groups and then reacting this intermediate with nitric oxide, NO. For example, by reacting cyclomatic Grignard reagent such as cyolopentadienyl magnesium bromide, with a nickel compound such as EXAMPLE I Under a nitrogen atmosphere, 1.82 moles of sodium cyclopentadiene, dissolved in te-trahydrofuran, were reacted with 0.91 mole of anhydrous nickel chloride. The reaction mixture was stirred at room temperature for 18 hours, then heated to reflux for four hours. Most of the tetrahydrofuran was removed by distillation, the remainder by heating in a steam bath with stirring under reduced pressure. The residue was sublimed under full vacuum. Over a 36 hour period, 56.0 parts of dicyclopentadienyl nickel were collected representing a 34.2 percent conversion based on the nickel chloride.
Under a nitrogen atmosphere, 0.29 mole of the dicyclopentadienyl nickel was dissolved in 500 ml. of petroleum ether boiling in the range of 385-50" C. Nitric oxide was bubbled into the dicyclopentadienyl nickel solution for 1.5 hours. After stirring for one hour, brown-green solids settled out, leavin a dark red solution which was filtered. The red filtrate was distilled in a helix-packed column at atmospheric pressure to remove most of the petroleum ether. The remainder was removed under slightly reduced pressure. Fractionation yielded 30 parts of cyclopentadienyl nickel nitrosyl representing 55 .8 percent conversion based on the dicyclopentadienyl nickel.
This stable, volatile, gasoline-soluble product is a deep red liquid boiling at 56.5 C./22 mm.
Analysis-Cale. for C H NiNO: Ni, 38.2. Found: Ni, 37.6.
This product along with the other additives is readily soluble in hydrocarbons and most organic solvents including hexane hydrocarbon fuels such as kerosene and diesel fuels, lubricating oils, alcohols, ether, acetone, ethylene glycol, etc.
In the above method of preparation, good results are also obtained in the manufacture of other compounds of this invention such as indenyl nickel nitrosyl, ethylcyclopentadienyl nickel nitrosyl, methylcyclopentadienyl nickel nitrosyl, and the like.
When compounds of the type described above are blended with liquid hydrocarbon distillate fuels to contain from about 0.001 to about 1 Weight percent of nickel spectacular results are obtained in the alleviation of soot formation with increase of burning efiiciency.
The base fuels employed in the compositions of this invention are generally liquid or semi-solid hydrocarbon compositions derived by distillation from crude petroleum and include those distillation fractions suitable for use in various burning functions which produce light and/ or heat in a system other than a spark ignition internal combustion engine as well as the residue fractions from such distillations. Thus the distillate fuels generally have initial evaporation temperatures of about 105 F. and final boiling points of from about 373 F. to about 700 F.
- These fuels have been designated in the art by various terms which are ordinarily indicative of their boiling range and other physical properties and the use to which the fuel is to be put. However, for any given fuel designation thereare ordinarily a variety of somewhat varied specifications which are applicable. The common names applied to the liquid hydrocarbon fuels employed in this invention include lamp oil, heating oil, kerosene, light petroleum distillate, stove oil, gas oil, household heating fuels, light industrial fuels, heavy industrial oils, stove and lamp naphtha, Number 2 heater fuel or furnace oil, diesel fuels (which may alternatively be employed in heating functions), and the like. In addition, other designations well known to those skilled in the art have been employed to characterize the fuels employed in the compositions of this invention. In general however, it may be stated that these fuels differ from gasoline not only in the use to which they are put but in their physical properties. Gasoline, for example, is a specific cut or blend of petroleum hydrocarbons which has a maximum initial boiling point up to about F. and a final boiling point never in excess of about 440 F. In addition, gasoline ordinarily has a flash point below 32 F. whereas the fuels employed in the compositions of this invention ordinarily will not flash below about 100 F. Furthermore, the great majority of fuel compositions employed in this invention have initial boiling points in excess of F.
The residual hydrocarbon fuels of this invention are in general high boiling liquid or semi-solid products which comprise the residue from primary distillation of crude oil or petroluem. Their main use is in fuels for industry boilers. In general, they have flash points of IOU-200 F., maxim-urn pour points of 15 F. and viscosities ranging between 70 and 500 SUS at 100 F. Such residual fuels include the well known bunker fuels such as No. 6 fuel oil which consists essentially entirely of residual material and No. 5 fuel oil which is made up of cracker or straight run residual fuel cut back with varying amounts of distillate fuel oils of the type described above.
The efficiency of the present compositions can be demonstrated as follows: A wick-type burner lamp, of the type ordinarily used for determination of sulfur in gasoline burns the fuel and produces soot. The burner must be carefully controlled to produce reproducible amounts of soot. Control is accomplished by centrally positioning the burner in a short, cylindrical vertical glass mantle. The burner-mantle assembly, in turn, is centrally positioned Within a longer, cylindrical vertical glass chimney. A base for the entire assembly contains grooves for the precise location of all parts, and also provides ports to admit air into the burner and chimney. Soot is collected on a steel plate suspended horizontally above the flame at the top of the chimney. This plate partially covers the top of the chimney, but leaves a small opening for exit of combustion gases.
In operation of the burner, the wick of the lamp is carefully trimmed square with a constant height of 0.5 cm. A constant weight of fuel, either with or Without an additive of this invention, is added to the lamp. The lamp is then allowed to stand without burning for about 2 hours in order to assure uniform adsorption of the fuel by the wick. Then the burner, mantle, and chimney are positioned on the base and the wick lighted. After 30 seconds, the steel collector is put into position on the chimney top and soot collected for 8 minutes. During this period from about 1.0 to 1.2 grams of fuel is burned. The collector plate then is carefully removed al id the flame extinguished. The soot is scraped from the plate and weighed. The Weight of fuel burned by the iamp is determined. by weighing the lamp before and after test. To eliminate the effect of minor variations in amounts of fuel consumed during various tests, the results are expressed as a soot factor, calculated as follows:
Soot collected, milligrams F Fuel burned, grams Soot factor Additive 8 Minute Tests Soot factor None 64.8 Do 60.2 Do 60.9 Do 60.7 Do 61.8 Do 63.5 Do 61.2 D 61.9 Average 61.9
.15 -g./gal. Ni as cyclopentadienyl Ni nitrosyl 35 .20 g./ gal. Ni as cyclopentadienyl Ni nitrosyl 29 .47 =g./ gal. Ni as Cyclopentadienyl Ni nitrosyl 9.2 .94 g./ gal. Ni as Cyclopentadienyl Ni nitrosyl 5.0
Similar results are obtained with other amounts of this additive within the range of concentration described above. Good results are also obtained in other distillate and residual fuels of this invention and with other additives of this invention.
A further demonstration of the remarkable properties of our additives is provided by their activity in cutting down carbon formation in diesel fuel. This is shown by the following data: The engine was a standard single cylinder ASTM diesel engine operated under CFR Method F--543 except that the fuel flow rate was 15 cc. per minute instead of 13 cc. per. minute. To the exhaust system of the engine was attached a bypass line provided with a fiberglass filter for collection of carbon particles from the exhaust stream. The filter and the lines leading to it were held by external heating at a temperature of 212 F. By means of a valve in the by-pass line the exhaust from the engine could be directed through a filter for a specified length of time. After each run the amount of carbon collected on the filter was determined by conventional analytical methods.
The fuel used was a conventional diesel fuel. In several runs in which the exhaust was run through the filter at the rate of approximately 6 liters per minute until 50 liters of exhaust gas had been passed through the filter, cyclopentadienyl nickel nitrosyl exhibited remarkable effectiveness in decreasing carbon formation. For example, at a concentration of cyclopentadienyl nickel nitrosyl equivalent to 0.105 gram of nickel per gallon the amount of reduction 'of carbon in the exhaust was 22 percent. This reduction was increased to 90 percent at a nickel concentration of 1.68 grams per gallon.
Similar results are obtained with other additives of this invention. Use of these additives permits not only a substantial smoke reduction but as an alternate permitsv the obtaining of more power from the diesel engine for a given smoke level.
The following examples, in which all parts and percentages are by weight, illustrate various specific em bodiments of the compositions of this invention employing fuels described above.
EXAMPLE II To :a typical petroleum derived kerosene (1000 parts) having an initial evaporation temperature of 325 F. and a final evaporation temperature of 565 F. is added with agitation 17.9 parts cyclopentadienyl nickel nitrosyl. The agitation is continued until a homogeneous blend containing 0.001 weight percent of nickel is achieved. The resulting fuel composition when employed in kerosene lamps or jet burners is found to have superior combustion characteristics than the fuel which contains no additive.
EXAMPLE III To 10.000 parts of a hydrocarbon fuel designated as No. 1 heater oil which has an initial evaporation temperature above 350 F. is added methylcyclopentadienyl nickel nitrosyl in amount sufficient to give a composition of about 1 percent nickel by weight.
EXAMPLE IV To 1000 parts of fuel suitable for use in jet burners having a 10 percent evaporation point of 220 F., a 90 percent evaporation temperature of 470 R, an end point of 550 F. and an API gravity of 45 is added a sufiioient quantity of octyl cyclopentadienyl nickel nitrosyl to give a fuel composition containing 0.002 percent by weight of nickel. This fuel is found to have improved combustion characteristics over the corresponding fuel without the octyl cyclopentadienyl nickel nitrosyl in that it burns with a cleaner flame at a higher fuel consumption rate and leaves a minimum of deposits on the interior surface of the apparatus in which it is used.
EXAMPLE V To 1000 parts of a furnace oil designated as No. 2 heater oil which has an initial evaporation temperature in excess of 380 F. is added with agitation sufficient indenyl nickel nitrosyl to give a composition containing 0.01 weight percent nickel.
EXAMPLE VI An improved kerosene blend according to this invention is prepared by adding to 1000 parts of a kerosene having a 10 percent evaporation point of 380 F. and a 90 percent evaporation point of 480 F., sufficient ethylcyclopentadienyl nickel nitr-osyl to give a composition containing 0.3 weight percent nickel.
EXAMPLE VII EXAMPLE VIII To a. fuel suitable for use in jet burners having a 10 percent evaporation point of 160 F.-and an end point of 600 F. is added cyclopentadienyl nickel nitrosyll in amount sufficient to produce a final composition containing 0.07 percent nickel which is eminently suited for use as a fuel in jet engines.
EXAMPLE IX Ethyl methylcyclopentadienyl nickel nitrosyl, in amount suificient to give a composition containing 1.5 weight percent nickel is added to a fuel suitable for use as a heater or diesel fuel. This fuel has an initial evaporation temperature of 350 F. and an end point of'580 F. When employed either in heating or diesel applications it is found to be a cleaner burning fuel than the base fuel without ethyl methylcyclopentadienyl nickel nitrosyl. EXAMPLE X Cyclopentadienyl nickel n-itrosyl is added to a residual fuel oil having a flash point of 160 F., a pour point of 10 F. and a viscosity of 300 SUS F.) in amount such that the nickel concentration is 0.001 weight percent.
EXAMPLE XI Methylcyclopentadienyl nickel nitrosyl is added to a light diesel fuel consisting of straight r-un gas oil out from paraffinic crude in amount such that the concentration of nickel is 0.3 weight percent.
In many applications petroleum distillate and residual fuels heavier than gasoline are employed in conjunction with other additives beside the cyclopentadienyl nickel nitrosyl compounds as employed in this invention for improving the burning efficiency of the fuel. These other aliases 6' additives usually comprise antioxidants, dyes, stabilizers, dispersants, corrosion inhibitors, cetane improvers, sludge inhibitors, and the like. It is therefore within the purview of this invention to employ hydrocarbon distillate and residual fuels heavier than gasoline containing a cyclopentadienyl nickel nitrosyl compound in conjunction with such additives. Typical of the antioxidant materials employed are alkylated phenols such as 2,6-di-tcrt-butyl phenol, 4,4'-rnethylene bis-2,6-di-tert-butyl phenol, 4- amino-2,6-di-tert-butyl phenol, and 2,6-di-tert-butyl-4- methyl phenol and amines such as N,N-di-sec-butyl pphenylenediamine and p-n-butylarninophenol. A typical sludge inhibitor is a copolymer of lauryl methacrylate and diethylarnino ethylmethacrylate, while various amines and sulfonates are often employed as dispersants. Typical cetane improvers are alkyl nitrates, such as arnyl nitrate and nitrates of polyhydric alcohols and ether-alcohols. I
In addition various phosphorus and boron compounds are frequently employed to impart improved stability to the fuels.
This application is a continuation-in-part of application Ser. No. 770,290, filed October 29, 1958, now US. Patent 3,006,742, which is a continuation-in-part of application Ser. No. 698,905, filed November 26, 1957, which in turn is a continuation-in-part of application Ser. No. 325,224, filed December 10, 1952, now US. Patent 2,818,416.
Having fully described the compositions of the present invention, modes for their employment and benefits derived therefrom, it is not intended to be limited except within the spirit and scope of the appended claims.
1. A liquid hydrocarbon distillate fuel heavier than gasoline adapted for use as an agent to produce light and heat when burned in a light or heat generating apparatus containing from 0.002 to 0.3 weight percent of nickel as a cyclopentadienyl nickel nitrosyl compound wherein the cyclopentadienyl group is a cyclopentadienyl hydrocarhon group which contains from 5 to about 13 carbon atoms.
2. A liquid hydrocarbon distillate fuel heavier than gas adapted for use as an agent to produce light and heat when burned in a light or heat generating apparatus containing from 0.001 to 1 weight percent of nickel as a cyclopentadienyl nickel nitrosyl compound wherein the cyclopentadienyl group is a cyclopentadienyl hydrocarhon group which contains from 5 to about 13 carbon atoms.
3. The composition of claim 2 wherein said compound is cyclopentadienyl nickel nitrosyl.
References Cited in the file of this patent UNITED STATES PATENTS 2,560,542 Bartleson et a1 July 17, 1951 2,591,503 Bottoms Apr. 1, 1952 2,818,416 Brown et al Dec. 31, 1957 FOREIGN PATENTS 1,140,411 France Mar. 4, 1957 555,282 Canada Apr. 1, 1958