Classifications

• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/103—Liquid carbonaceous fuels containing additives stabilisation of anti-knock agents
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/20—Organic compounds containing halogen
  • C10L1/201—Organic compounds containing halogen aliphatic bond
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/20—Organic compounds containing halogen
  • C10L1/202—Organic compounds containing halogen aromatic bond
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/30—Organic compounds compounds not mentioned before (complexes)
  • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
  • C10L1/306—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond) organo Pb compounds

Definitions

• This invention relates to a class of bromo-hydrocarbon compounds for use as scavengers with lead antiknock compounds, having a particular molecular structure and a particular vapor pressure which make them superior to scavengers heretofore known or used.
• These scavengers may be used alone in lead-treated fuels generally and are preferred for use in aviation fuels.
• a preferred motor fuel contains both bromoand chloro-hydrocarbon scavengers.
• our invention is a mixture of one or more of our bromo-hydrocarbons with one or more chloro-hydrocarbons having a particular vapor pressure.' I
• Scavengers are materials employed with lead antiknock compounds in fuels for internal combustion engines to produce, during combustion, volatile lead compounds which are exhausted from the engine. Scavengers reduce the amount of the less volatile lead compounds which otherwise form during combustion and collect on engine parts. For satisfactory operation of an engine employing leaded gasoline, it is essential that a scavenger be used. Commercially used scavengers are ethylene dibromlde and ethylene dichloride.
• our bromine compounds give superior results in engines in many situations within the wide range of conditions encountered in service.
• our scavengers have molecular structures which, under many engine operating conditions, result in the bromine contained therein having in the engine cylinder a unit effectiveness superior to that of the scavengers heretofore used commercially.
• This property of efiectiveness within the cylinder we call intrinsic scavenging emciency of characteristic in fuel the compound.
• Our scavengers in addition to high intrinsic scavenging eflicienc other advantages. These. include an evaporation such as to give a suitable pattern of distribution in the engine relative to that of lead antiknock compounds under the range of intake manifold conditions encountered in service, high inherent stability when stored in admixture with lead antiknock compounds. and ready miscibility with lead antiknock agents.
• our scavengers are many which have only a slight tendency to reduce the antiknock effectiveness of the lead compound in the engine.
• Our invention is the use as scavengers of the class of bromine-substituted hydrocarbons having two to three bromine atoms and from three to eight carbon atoms inclusive, having not more than one bromine atom attached to any carbon atom, and having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury.
• Our invention also includes the use of these scavengers with chloro-hydrocarbons having a vapor C. of substantially 0.2 to 6 millimeters of mercury.
• bromo-hydrocarbons for use with the lead compounds in aviation fuels and of a mixture of bromo-hydrocarbons and chlorohydrocarbons for use with the lead compounds in motor fuels merely follows present commercial trends in the use of scavengers. Such use appears to give best results.
• the quantity of scavenger theoretically required for reaction with the lead to form the lead halide which quantity is two atoms of halogen per atom of lead, is called one theory of halogen.
• Present commercial practice is to use one theory of bromine in aviation fuels, while for motor fuels one-half theory of bromine is used with one theory of chlorine.
• the scavengers were used in amounts providing the number of theories of halogen employed in commercial practice.
• our scavengers were employed in heavy-duty operation of a fleet of commercial trucks. 1,2,3-tribromopropane, in combination with hexachloropropylene, was blended with tetraethyllead and incorporated in a gasoline which was used in part of the fleet. A treated fuel consisting of the same base gasoline containing tetraethyllead and a mixture of ethylene dibromide and ethylene dichloride as the scavenger was used in the remainder of the fleet. Since the conditions were identical except for the scavenger composition, any difference in lead deposits and corrosion of the engines was attributable to the differences in the scavengers.
• Each of the trucks was operated on a twenty-four hour per day basis while carrying a gross load of about 32,000 pounds.
• the exhaust valve life based on miles to the first two valve failures in each engine, on the average was 30% greater for the trucks operating on the fuel containing our scavengers than on the fuel containing the commercial mixture of ethylene dibromide and ethylene dichloride.
• the durability of exhaust valves is a critical factor, and improvements of the above magnitude are of great importance to the owners of trucks and busses, because of decreased expense of maintenance and greater availability of the vehicles for operation on the road.
• Our scavengers have also been used with greatly improved efliciency in commercial aircraft engines operated under conditions comparable to those encountered in flight.
• highoutput liquid-cooled aviation engines operated with three difierent scavengers, namely ethylene dibromide, 1,2,3-tribromopropane and mixed dibromotoluenes, the last two being scavengers of our invention.
• Each operation' was hours in duration on a fuel containing 4.6 milliliters of tetraethyllead per U. S. gallon and 1.0 theory of one of the above-named bromo-hydrocarbon scavengers.
• the concentration of tetra ethyllead in the liquid portion of the fuel' flowing along the manifold walls is generally far higher than that in the original fuel, so that a considerable part of the total quantity of tetraethyllead input may remain in the relatively small amount of liquid on the manifold walls. If this liquid portion of the fuel does not distribute evenly, some cylinders receive widely disproportionate amounts of tetraethyllead. In certain types of operations we have found variations in tetraethyllead input to motor vehicle cylinders of as much as 50%. Much wider variations have been found in aircraft engines, the tetraethyllead input to individual cylinders varying from 45% to 400% of the average amount.
• the pattern of distribution of the scavenger to the engine cylinders may be entirely different from that of the tetr :thyllead.
• the scavengers of our invention follow the lead more close- 1y than the scavengers presently used.
• the boiling point of a scavenger is not a reliable index of its evaporation relative to that of tetraethyllead in the engine manifold.
• 1,2,3-tribromopropane having a boiling point 20 C. higher than that of tetraethyllead, would normally be expected to evaporate less readily and to cause the concentration of bromine to be more than one theory in the liquid which flows along the walls of the manifold.
• the liquid flowing along the walls of the manifold contained sustantially less than one theory of bromine.
• antiknock fluids containing scavengers are highly important to the shipping and storing of such fluids, either alone or in gasolines. Under normal storage or shipping conditions, antiknock fluids containing lead compounds may decompose to a, slight extent even when the most stable scavengers are incorporated. When lead antiknock fluids or fuels containing lead antiknock fluids are to be stored for periods of several years, especially at elevated temperatures, it is desirable that the stability of the antiknock fluids be high.
• the stability of the antiknock fluid mixture may be temporarily improved by the addition of certain antioxidants, such as the alkylsubstituted phenol of Walters Patent No. 2,361,- 377.
• certain antioxidants such as the alkylsubstituted phenol of Walters Patent No. 2,361,- 377.
• many of the bromo-hydrocarbons whose molecular structure does not conform to our speciflcation, such as 1,l,2,2-tetrabromoethane are so unstable with tetraethyllead, even with the addition of antioxidants, as to be unsatisfactory for commercial use as scavengers.
• halogen compounds which might be considered for use as scavengers are unsatisfactory because they react in the engine with the lead antiknock compound to reduce the antiknock effectiveness of a given concentration of the lead antiknock compound.
• Our scavengers vary in this respect. The number of scavengers from which to make'a selection is large enough so that compounds can be selected which do not decrease antiknock effectiveness materially.
• a desirable property for a commercial scavenger is complete miscibility with the lead antiknock compounds, down to low temperatures. so that the mixture will not separate when stored and handled in cold weather. If desired, the minimum temperature of complete miscibility may be lowered, by the addition of a mutual solvent.
• same eifect may also be achieved by using, instead SAW 9 of a single scavenger, a mixture of two or more scavengers.
• our scavengers may be used with lead compounds other than tetraethyllead, such as tetrapropyllead, dimethyldiethyllead, and methyltriethyllead.
• lead antiknock compounds
• the scavenger may be one of our bromo-hydrocarbons or a mixture of two or more of them. It is customary to make a blend of the lead antiknock compound and the scavenger and then to add this mixture to a gasoline. However, the scavenger and antiknock compound may be added separately to the fuel.
• our scavengers vary sumciently to permit a selection for any specific conditions of use. For example, where storage stability is of prime importance the bromo-aromatic scavengers of our invention may be selected, while if high intrinsic scavenging ability is most desired our saturated bromo-aliphatic hydrocarbon scavengers are preferred. Where distribution in the engine relative to that of tetraethyllead is the principal problem, our scavengers having a vapor pressure between 0.5 and 2 millimeters of mercury at 50 C. are preferred.
• the proportions of scavengers used in the above examples have been the same, i. e., one theory of bromo-hydrocarbon ior the lead compounds in aviation gasolines, and a mixture of one-half theory of a bromo-hydrocarbon and one theory of a chloro-hydrocarbon for the lead compounds in motor fuels.
• the use of our scavengers is not critical, and therefore is not so limited.
• For aviation fuels best results have been obtained with proportions varying from 0.8 theory to 1.5 theories, and a wider variation i may be used.
• proportions of scavengers set forth in Bartholomew Patent No. 2,898,281.
• An antiknock composition consisting essentially of a lead antiknock compound and a scavenger in an amount sufllcient to reduce the deposition of lead in the engine by forming volatile lead compounds, a principal active scaveng-- ing ingredient of which is a bromo-hydrocarbon having two to three bromine atoms and from three to eight carbon atoms inclusive, having not more than one bromine-atom attached to any carbon atom, and having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury.
• An antiknock composition consisting essentially of tetraethyllead and a scavenger in an amount suflicient to reduce the deposition of lead in the engine by forming volatile lead compounds, a principal active scavenging ingredient of which is a bromohydrocarbon having two to three bromine atoms and from three to eight carbon atoms inclusive, having not more than one bromine atom attached to any carbon atom, and having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury.
• An antiknock composition consisting essentially of a lead antiknock compound and a scavenger in an amount sufficient to reduce the deposition of lead in the engine by forming vo atile lead compounds, a principal active scaveng ing ingredient of which is a bromo-hydrocarbon having two to three bromine atoms and from three to eight carbon atoms inclusive, having not more than one bromine atom attached to any carbon'atom, and having a vapor pressure at 50 C ofsubstantially 0.5 to 2 millimeters of mercury.
• An antiknock composition consisting essentially of a lead antiknock compound and approximately one-half theory of a bromo-hydrocarbon scavenger having two to three bromine atoms and from three to eight carbon atoms inclusive, having not more than one bromine atom attached to any carbon atom, and having a vapor pressure at 50 C. of substantially 0.5 to 2 millimeters of mercury, in admixture with approximately one theory of a chloro-hydrocarbon having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury.
• composition of matter as defined in claim 1 wherein the bromo-hydrocarbon is a saturated bromo-aliphatic hydrocarbon.
• composition of matter as defined in claim 1 wherein the bromo-hydrocarbon is a bromocycloaliphatic hydrocarbon.
• composition of matter as defined in claim 1 wherein the bromo-hydrocarbon is a bromoaromatic hydrocarbon.
• An antiknock composition consisting essentially of a lead antiknock compound and a scavenger in an amount sumcient to reduce the. deposition of lead in the engine by forming volatile lead compounds, a principal active scavenger ingredient of which is dibromobenzene.
• An antiknock composition consisting essentially of a lead antiknock compound and a mixture of scavengers each of which is present in an amount sufficient to reduce the deposition of lead in the engine by forming volatile lead compounds, the principal active scavenging ingredients of which are a bromo-hydrocarbon having two to three bromine atoms and from three to eight carbon atoms inclusive, having not more than one bromine atom attached to any carbon atom, and having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury, and a chloro-hydrocarbon having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury.
• An antiknock composition consisting essentially of a lead antiknock compound and a mixture of scavengers each of which is present in an amount suflicient to reduce the deposition of lead in the engine by forming volatile lead compounds, the principal active scavenging ingredients of which are 1, 2, 4-trichlorobenzene and a bromo-hydrocarbon having two to three bromine atoms and from three to eight carbon atoms inclusive, having not more than one bromine atom attached to any carbon atom, and having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury.
• An antiknock composition consisting essentially of a lead antiknock compound and a scavenger in an amount suflicient to reduce the deposition of lead in the engine by forming v01- atile lead compounds, a. principal active scavenging ingredient of which is dibromotoluene.
• An antiknock composition consisting essentially of a, lead antiknook compound and a mixture of scavengers each of which is present in an amount suflicient to reduce the deposition of lead in the engine by forming volatile lead compounds, the principal active scavenging ingredients of which are dibromotoluene, and a chloro-hydrocarbon having a vapor pressure at 50 C. of substantially 0.2 to 6 millimeters of mercury.
• An antiknock composition consisting essentially of a lead antiknock compound and a mixture of scavengers each of which is present in an amount suflicient to reduce the deposition of lead in the engine by forming volatile lead 8,170,000 11 12 compounds, the principal active scavenging 1ngredients of which are dlbromotoluene and 1, 2, m PAW 4-tr1ch1orobenzene.
• Number Name Due GEORGE CALINGAER'I'. l 1,688,022 Mldzley, Jr. May 1, 1928 JOHN S. WINTRINGHAM. 5 2,384,921 Bhokal Dec. 12, 1944 2,4!1328 Wlczer Aug. 24, 1948 REFERENCES CITED The following references are of record in the file of this patent:

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Citations (3)

• 0
  • BE BE489214D patent/BE489214A/xx unknown
  • BE BE489213D patent/BE489213A/xx unknown
• 1948
  • 1948-07-24 US US40625A patent/US2479900A/en not_active Expired - Lifetime
• 1949
  • 1949-04-28 GB GB11304/49A patent/GB679623A/en not_active Expired
  • 1949-05-04 GB GB11899/49A patent/GB682385A/en not_active Expired
  • 1949-05-10 DE DEP42241A patent/DE822030C/de not_active Expired
  • 1949-05-11 DE DEP42348A patent/DE843038C/de not_active Expired
  • 1949-05-12 FR FR986121D patent/FR986121A/fr not_active Expired
  • 1949-06-03 CH CH282390D patent/CH282390A/fr unknown
  • 1949-06-24 CH CH293437D patent/CH293437A/fr unknown

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