|Publication number||US3346354 A|
|Publication date||Oct 10, 1967|
|Filing date||Jul 2, 1963|
|Priority date||Jul 2, 1963|
|Publication number||US 3346354 A, US 3346354A, US-A-3346354, US3346354 A, US3346354A|
|Inventors||George J Kautsky, Eddie G Lindstrom|
|Original Assignee||Chvron Res Company|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (9), Referenced by (55), Classifications (6)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,346,354 LONG-CHAIN ALKENYL SUCCI'NIC ACIDS, ESTERS, AND ANHYDRIDES AS FUEL DETERGENTS George J. Kautsky, El Cerrito, and Eddie G. Lindstrom,
Martinez, Calif., assignors to Chevron Research Company, a corporation of Delaware No Drawing. Filed July 2, 1963, Ser. No. 292,450
3 Claims. (CI. 44-63) ABSTRACT OF THE DISCLOSURE This invention is concerned with fuel compositions having incorporated therein metal free detergent additives. More particularly it is concerned with fuel compositions containing as deposit-suppressing detergent additives, alkenyl succinic acids, anhydrides and esters.
In recent years spark-ignition internal combustion engines have been designed and built by the industry with the emphasis being placed upon higher ratios, larger engines and high volumetric efiiciency at high speeds. Volumetric efiiciency is dependent upon such factors as unhindered flow of fuel-air mixtures through valves and ports, and the maintenance of high compression by eflicient valve closure and timing. However, most fuels in use today when employed in such engines undergo deterioration and leave hard carbonaceous deposits on intake valve underheads and stems and in the valve ports, interfering with proper valve seating and causing a consequent loss of power and thus requiring frequent maintenance in order that engines may develop their maximum efficiency as to power and fuel consumption. These deposits result in part from puff-back of decomposition products from the compression chamber and in part from decomposition of crankcase oil entering by way of the valve stem. The deposits may also contain lead compounds that result from the decomposition of leadcontaining octane improvers. These deposits attach firmly to the valves and ports and the fuel detergents that are in current use in fuels have little or no effect in either reducing the deposits already formed or preventing the formation of new harmful deposits.
In addition to the problems caused in spark-ignition engines, fuel deposits cause serious operational problems in compression ignition or diesel type engines. An especially serious problem is the deposition of lacquer and other carbonaceous materials within the fuel injector tips of such engines. These cause injector sticking, interfere with injector seating and alter the fuel spray patterns and thus ultimately affect the combustion of the fuel, reducing power and seriously affecting the economy of engine operation.
In the operation of turbine and jet type engines, fuel deposits which result from the high temperatures to which the fuels are subjected, cause serious problems resulting in the plugging of filters and causing poor heat exchange.
3,346,354 Patented Oct. 10, 1967 Therefore, there exists a serious need for additives which, when added in proper amounts to fuel compositions, will reduce deposit formation and even reduce deposits that are already present due to prior operation with fuels which have formed heavy deposits.
It has now been found that superior liquid hydrocarbon fuel compositions, resistant to harmful deposit formation result from the addition to the compositions of minor amounts of alkenyl succinic acids, the corresponding alkenyl succinic anhydrides, and the lower mono and dialkyl esters of said acids, wherein the alkenyl groups contain from 50 to 250 carbon atoms and the alkoxy groups of the esters contain from 1 to 6 carbon atoms.
Thus, the alkenyl succinic anhydrides mentioned above can be prepared by reacting maleic anhydride with a suitable polyolefin, preferably a polyolefin derived from olefins containing from 2 to 5 carbon atoms. Examples are ethylene, propylene, l-butene, 2-butene, isobutene and mixtures of said olefins. A preferred polyolefin is a polyisobutene having a molecular weight from about 400 to 3500 and more preferably from 800 to 3200.
The preferred compound is the (ii-tertiary butyl ester of a substituted succinic acid which is produced from polyisobutene having a molecular weight of about 3000.
In addition to the deposit suppressing and detergent qualities of the aforementioned compounds, they possess an additional desired characteristic in that they display good non-emulsifying properties in fuel compositions. A common defect of many surface-active additives is the property of forming undesirable emulsions of water with the hydrocarbon stocks in which they are employed. The emulsion formation is effectively suppressed by use of compounds such as the tertiary-alkyl esters and the polyisobutenyl succinic anhydrides of this invention, which represent especially desirable classes of compounds, imparting excellent detergency characteristics, and no emulsifying properties to the compositions.
The effective amount of the additive that must be added to impart the desired anti-deposit characteristics will vary according to the nature and use of each particular base fuel, however, in general, amounts from 50 p.p.m. to 1000 p.p.m. are suflicient, and under most circumstances an amount from 50 to 500 p.p.m. is preferred.
The addition to the fuel compositions of a minor proportion of a light petroleum oil in addition to the abovedescribed compounds further enhances the deposit-suppressing effect and makes it possible to reduce the amount of succinic acid derivative in the compositions and achieve a like desirable reduction of deposit formation. The light petroleum oil may be any low viscosity petroleum oil fraction, preferred examples being neutral oils in the range of from 50 to 480 SSU at F. A specific example is an oil having a viscosity of 60 SSU at 100 F. The use of these oils in minor proportions from 5,000 to 15,000 p.p.m. is effective, a preferred amount being in the range of from 5,000 to 10,000 p.p.m.
The succinic acid derivatives of this invention may be prepared by reactions well known in the art. The polymerization of olefins is especially well-known and the method employed has no effect upon the compounds described herein and thus any available process may be used for this step.
The aforementioned reaction of tit-polyolefin and maleic anhydride to produce an alkenyl succinic anhydride can 3 be described by the following formulae, using polyisobutene as an example:
in which n is an integer from about 10 to about 60.
The production of alkenyl succinic acids from their corresponding anhydrides may be effected by any known method of hydrolysis, i.e., heating with water, acid hydrolysis, etc.
Thus the reaction can be carried out using molar ratios of polyolefin to anhydride of from 1:1 to 1:10 and preferably from 1:1 to 1:5. The reaction temperature may vary from 300 to 500 F., a range of from about 425 to 475 F. is preferred because of the high yields obtained.
The esterification reaction used to produce the ester derivatives of this invention may be carried out by any commonly used method. For example, acid catalyzed esterification with alcohols or oxides, or reaction with olefins in the presence of acid catalysts, such as sulfuric acid.
The aforementioned alkenyl succinic esters may be produced by reaction of the acids with alcohols or the anhydrides with alkylene oxides. 4
Reaction of the anhydrides with alcohols results in the formation of a mono ester or acid ester in which one carhoxyl radical is not esterified. Both the mono and diesters show good detergent effect and the above-mentioned methods of esterification are highly desirable methods, with high yields, yields of from 80% to near 100% being common. The production of the mono esters by reaction of anhydrides with alkyl oxides is essentially quantitative.
The following examples illustrate the preparation of the additives of this invention. The examples are intended to be only illustrative and not limiting. Amounts are on a weight basis unless otherwise specified.
Example I.Preparation of polyis'obutenyl succinic anhydride 1 mole of polyisobutene, having an average molecular weight of 1000, was placed in a 3-neck 2-liter flask equipped with a thermometer, mechanical stirrer and reflux condenser. The material was heated to 240 C. at which point molten maleic anhydride was added dropwise at such a rate that a temperature of 240 C. was maintained without further heating. Two moles of maleic anhydride were added over the course of 6 hours. The excess maleic anhydride was then stripped from the reaction mixture under vacuum. The reaction product was diluted with 150 neutral oil and filtered through diatomaceous earth to remove a small amount of by-products. The yield of anhydride was 860 g. or 80% of theoretical based upon polyisobutene.
Example II.Preparatin of polyisobutenyl succinic acid 1 mole of polyisobutenyl succinic anhydride, prepared by the process described in Example I, was heated with 2 moles of water for a period of 6 hours at 100 C. The mixture was allowed to cool and the water layer was discarded. The yield of acid was 95% based upon the weight of anhydride.
Example Il1.-Preparation of di-tertiarybutyl ester of polyisobutenyl succinic acid An amount of a 30% solution of polyisobuentyl succinic acid in 150 neutral oil, sufficient to supply 1 mole of the acid, was dissolved in 2 volumes of ethyl ether and volume of concentrated H 50 and placed in a reaction flask. An excess of 2 moles of isobutene was added and the mixture was shaken for a period of 12 hours under a pressure of 50 psi. at 25 C. The mixture was then washed with hot H 0 and the excess H neutralized with solid Na CO The mixture was washed repeatedly with H 0 and then the ether stripped from the mixture and the remaining H O removed as a separate phase. Yield of the ester was 86% based upon amount of acid charged.
Example I V.-Preparati0n of polybatenyl methyl acid saccinate 2 moles of methanol were mixed with 1 mole of polyisobutenyl succinic anhydride prepared according to Example I. The mixture was heated to 60 C. and held for 2 hours. The excess of methanol was removed under vacuum. Yield of the half ester was essentially equal to theoretical.
Example V.Preparation of polyz'sobutene di-n-butyl succinate 1 mole of polyisobutenyl succinic anhydride and 6 moles of n-butanol were placed in a reaction flask equipped with a thermometer and reflux condenser. The mixture was allowed to reflux for 2 hours. One mole of B 0 was then removed by slow distillation of the excess alcohol. The product was di-ester and 5% monoester.
The detergent effect of the additives of this invention was demonstrated in the case of spark-ignition engine fuels in a simulated urban-suburban laboratory engine test and in actual automobile tests. A diesel engine test was used to demonstrate effectiveness in diesel type fuel and a modified ASTM-CRC Fuel Coker Test (D-1660) was used to determine suppression of high temperature deposit formation and filter plugging in jet fuels.
The simulated urban-suburban engine test mentioned above is a test designed to duplicate the conditions encountered in every day stop-and-start driving. The engine used was a F-956 Chevrolet V-8 of 283 cubic inch displacement. The engine was cycled in a pattern under the following running conditions:
Each cycle was repeated eight times, after which the engine was shut down for 3 minutes, restarted, and the cycles repeated. The complete test was hours.
At the end of the test, the engine was dismantled and the intake valves and ports were visually inspected for deposits. A rating scale of 0 to 10 was used, a rating of 0 indicating a perfectly clean valve or port and 10 indi-. cating very heavy deposits. The deposit from each valve was also weighed.
The gasoline used in the test was of premium grade and contained 2.06 ml. per gallon of tetramethyl lead. The four different base fuels used are indicated by letter A through D. The polyisobutenyl succinic acid which is referred to as PIBSA, and the derivatives thereof listed in the following table contained about 60 carbon atoms in the alkenyl radical. The oil which is referred to in the table was a light petroleum oil having a viscosity of 60 SSU at 100 F.
TABLE I.-URBAN-SUBURBAN CYCLE ENGINE TEST DATA Valves Test Compound Conc., Ports,
p.p.m. Rating Rating Deposit None (base fuel) 5.9 3.42 6.0 PIB SA 500 -0. 0. 29 0-0. 5 P13 SA 200 0. 4 0.28 0.0 None (ba 5.1 3.15 6.8 PIBSA 100 2.9 1.83 3.0 None (base fuel 4. 3 2. 32 5.6 7 1 7, 3.0 2.49 4.6 s PIBSA+Oil 100+7,000 0.9 0.92 0.7 9 None (base fuel) 3.6 1.67 4.0 10 Di-tert-butyl ester of 300+7,000 0.4 0.35 0.3
PIBSA+OiL 11 None (base fuel) 6.4 4.03 6.0 12 Di-n-butyl ester of 100+7,000 4.3 3.2 4.0
PIBSA+0iL PIB SA: Polyisobutenyl Succinic Acid.
It is apparent from the above data that the additives In the test procedure adopted, each engine was disof this invention impart surprising deposit-suppressing assembled and each intake valve and port was visually characteristics to spark-ignition engine fuels or gasolines rated for the amount of deposit on a scale from 0 to in which they are employed. These data show that the 10 with 0 representing a completely clean port and acids and the esters of this invention each display this 10 representing a Very heavy deposit. One valve and favorable characteristic and that the addition of a light port were removed and cleaned and the total weight of oil to the composition further enhances the detergent or deposit was determined, this figure representing the dispersant effect. It is also evident that the esters derived equilibrium deposit for the engine. The engine was refrom branched-chain alcohols, such as tertiary butyl alcoassembled and each auto was then driven for 5000 miles hol are superior to the derivatives of corresponding norunder ordinary urban-suburban operating conditions with mal alcohols such as n-butyl alcohol. a fuel composition consisting of a gasoline of the same In order to further demonstrate the detergent and detype previously employed in the auto and 500 ppm. of posit-suppressing characteristics of these additives when the additive being tested. At the end of the test period they are employed in spark-ignition fuels, fuel composieach engine was disassembled and the valve which had tions containing various of these additives and related been removed at the beginning of the test was visually compounds were evaluated under field test conditions in rated and cleaned, and again removed and the deposit private automobile engines. In the tests standard Ameriweighed. The difference between this weight of deposit can automobiles were employed. At the beginning of the and the previously determined equilibrium deposit is extest, each auto had been driven a sufiicient length of time pressed in terms of percent of equilibrium deposit in to accumulate an equilibrium deposit in the intake mani- Table II as Deposit Prevention. Negative values indifold and upon the intake valves. The equilibrium posit is the amount of deposit that is normally accumulated after extended operation with similar fuels. When this amount is deposited, it has been found that further cate a resulting deposit increase. The undisturbed valves which had been previously rated by inspection were rerated and the difference between the two deposit ratings is expressed in Table II as Deposit Reduction.
TABLE II.--DEPOSIT SUPPRESSION AND REDUCTION IN TEST AUTOMOBILES Deposit Levels Percent Deposit Deposits on Reduction Clean Valves Percent Deposit Compound Initial Rating Final Rating Preven- Be'ore A ter tion Valves Ports Cleaning Test Valves Ports Valves Ports Polyisobutenyl Succinic Anhydride (derived from Polybutene, average molecular wt. 1,000) 5. 9 3. 6 5. 2 2. 3 12 36 3. 2 2.0 40 Polyisobutenyl Succinic Acid (derived from Polybutene, average molecular wt. 1,000) 2. 7 2. 0 2. 6 1. 8 4 10 2. 0 1. 0 Polyisobutenyl Succinic Acid (derived from Polybutene, average molecular wt. 500) 5. 8 2. 6 5. 4 2. 0 7 23 5. 0 3. 0 40 Polyisobutenyl Suceinic Acid (derived from P0lybutane, average molecular wt. 3,000) 5. 9 3. 8 4. 4 2. 7 25 29 7. 8 2. 0 Monomethyl Polyisobutenyl Succinate (derived from Polybutene, average molecular wt. 1,000) 4. 9 3. 1 4. 2 2. 3 14 26 5. 3 2. 0 63 Octadecenyl Succinic Anhydride 4. 6 3.8 5.4 3. 5 18 8 2.0 6.0 *200 Tetrapropenyl Succinic Acid 4. 3 3. 2 4. 5 2. 6 *5 18 2. 5 6. 0
* Indicates deposit increase.
operation under normal conditions results in essentially no further build-up of carbonaceous material. Prior to the test each auto had been operated on a high grade The above data show that the additives of this invention display extremely good deposit suppressing and reducing properties under typical driving conditions. It will be noted that the compounds produced from low molecular weight polyolefins, as shown by the asterisk marked values, do not give these characteristics, instead, their addition results in a substantial increase of the already existing deposits and in the formation of new deposits in excess of the equilibrium deposit. Thus, the aforementioned detergent characteristics of the higher molecular weight derivatives are unexpected.
In order to demonstrate effectiveness of the additives of the present invention in reducing the amount of deposits in diesel engines, an engine test was performed using 200 ppm. of polyisobutenyl succinic anhydride in a base diesel fuel and comparing the weight of deposits resulting inside of the fuel injector tips with the deposit from the base fuel alone. Use of this additive resulted in a substantial reduction in weight of deposit.
In order to determine the utility of these additives in I jet fuels, a jet fuel containing 200 ppm. of polyisobutenyl succinic anhydride was tested in the modified CFR Fuel Coker Test which correlates with the ASTM CRC Fuel Coker Test (D-1660) and compared with the base fuel without additive. The modified test is run at a fuel passage rate of 2.8 lbs. per hour in contrast to 6 lbs. per hour for the standard ASTM test. The temperature of the modified test is 475500 F. as compared to the 300-400 F. operation temperature in the standard test. The test showed that the addition of minor amounts of the above-named compound eliminated filter plugging and substantially reduced preheater tube and filter discoloration.
Thus the use of the additives of this invention with spark-ignition fuels, compression ignition fuels and jet type fuels is specifically contemplated.
Spark-ignition fuels in which use of the present additives is contemplated are fuels in the gasoline boiling range, including hydrocarbon base fuels boiling substantially in the gasoline boiling range of from about 100 F. to about 450 F. These fuels may be leaded fuels, i.e. fuels containing lead alkyl additives such as tetraethyl lead, tetramethyl lead and like compounds which are introduced into the compositions to prevent preignition and engine knock.
Compression engine fuels or diesel type fuels are hydrocarbon base fuels, for example, distillate fuels cornprising a mixture of hydrocarbons boiling substantially in the range of from about 300 F. to about 750 F. and particularly from 350 to 700 F. Such fuels are commonly derived from crude petroleum oils, from shale oils, from synthetic hydrocarbons as example, from the Fischer-Tropsch synthesis, and from other sources.
Jet fuels.Fuels commonly employed in aircraft jettype and turbine engines are liquid hydrocarbons boiling substantially in the range of from about F. to about 650 F: The specific fuels vary according to the use and type of engine. Specific examples of the types of turbine and jet fuels are military grades such as J P4, the specified boiling range .of which is from F. to 550 F. and ]P5 with specified boiling range of from 326 F. to 550 F. An example of a commercial jet fuel is J P6 which has specification boiling limits of from 250 F. to 550 F. An example of aturbine fuel is commercial turbine fuel which has a boiling range between 260 F. and 406 F.
In addition to the additives of this invention, the use of other conventional fuel additives is contemplated. Thus the fuel compositions may also contain surfaceignition suppressants, such as phosphorus-containing compounds, dyes, gum inhibitors, and oxidation inhibitors.
What is claimed is:
1. A hydrocarbon fuel composition capable of reducing intake valve and port deposits comprising a major proportion of a distillate hydrocarbon mixture boiling substantially in the range of from 100 F. to 750 F. and from 50 to 1,000 ppm. of a succinic acid derivative selected from the group consisting of (A) an alkenyl succiuic acid,
(B) an alkenyl succinic anhydride, and
(C) an alkenyl succinic ester in which the alkoxy group contains from 1 to 6 carbon atoms, wherein the alkenyl groups (A), (B), and (C) contain from 50 to 250 carbon atoms.
2. The fuel composition of claim 1 in which the succinic acid derivative is the di-tertiary butyl ester of polyisobutenyl succinic acid.
3. The fuel composition of claim 1 in which the distillate hydrocarbon mixture is a spark-ignition fuel boiling substantially in the range of 100 F. to 450 F.
References Cited UNITED STATES PATENTS 2,312,790 3/1943 Backofi' et al. 4470 2,922,706 1/1960 Durr et al. 44-70 2,993,772 7/1961 StrOmberg 4470 2,993,773 7/1961 Stromberg 4470 3,031,278 4/1962 Buckrnann et a1 44-58 3,172,892 3/1965 LeSeur et al. 252-51.5 3,234,131 2/1966 Morway 25256 3,255,108 6/1966 Wiese 252-56 FOREIGN PATENTS 981,850 l/ 1965 Great Britain.
DANIEL E. WYMAN, Primary Examiner.
W. J. SHINE, Assistant Examiner.
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