US2747979A - Mono-esters of citric acid as metal deactivators for motor fuels - Google Patents
Mono-esters of citric acid as metal deactivators for motor fuels Download PDFInfo
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- US2747979A US2747979A US320607A US32060752A US2747979A US 2747979 A US2747979 A US 2747979A US 320607 A US320607 A US 320607A US 32060752 A US32060752 A US 32060752A US 2747979 A US2747979 A US 2747979A
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- citric acid
- mono
- gasoline
- esters
- copper
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims description 64
- 239000000446 fuel Substances 0.000 title claims description 16
- 239000006078 metal deactivator Substances 0.000 title description 9
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000009931 harmful effect Effects 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 15
- 229910052802 copper Inorganic materials 0.000 description 15
- 239000010949 copper Substances 0.000 description 15
- 230000006698 induction Effects 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 9
- -1 mercaptans Chemical class 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- SKHXHUZZFVMERR-UHFFFAOYSA-N 1-Isopropyl citrate Chemical compound CC(C)OC(=O)CC(O)(C(O)=O)CC(O)=O SKHXHUZZFVMERR-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- JHZLLXXZMYEPHT-UHFFFAOYSA-N 2-(2-cyclohexyloxy-2-oxoethyl)-2-hydroxybutanedioic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(=O)OC1CCCCC1 JHZLLXXZMYEPHT-UHFFFAOYSA-N 0.000 description 3
- VAMBUGIXOVLJEA-UHFFFAOYSA-N 4-(butylamino)phenol Chemical compound CCCCNC1=CC=C(O)C=C1 VAMBUGIXOVLJEA-UHFFFAOYSA-N 0.000 description 3
- 239000002310 Isopropyl citrate Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- SKHXHUZZFVMERR-UHFFFAOYSA-L isopropyl citrate Chemical compound CC(C)OC(=O)CC(O)(C([O-])=O)CC([O-])=O SKHXHUZZFVMERR-UHFFFAOYSA-L 0.000 description 3
- 235000019300 isopropyl citrate Nutrition 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- TWUZWTIVCCRAAD-UHFFFAOYSA-N 2-(2-butoxy-2-oxoethyl)-2-hydroxybutanedioic acid Chemical compound CCCCOC(=O)CC(O)(C(O)=O)CC(O)=O TWUZWTIVCCRAAD-UHFFFAOYSA-N 0.000 description 2
- WEKLUCWCJWZVGP-UHFFFAOYSA-N 2-(2-dodecoxy-2-oxoethyl)-2-hydroxybutanedioic acid Chemical compound CCCCCCCCCCCCOC(=O)CC(O)(C(O)=O)CC(O)=O WEKLUCWCJWZVGP-UHFFFAOYSA-N 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000005691 triesters Chemical class 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RURPJGZXBHYNEM-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]propyliminomethyl]phenol Chemical compound C=1C=CC=C(O)C=1C=NC(C)CN=CC1=CC=CC=C1O RURPJGZXBHYNEM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
- C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
Definitions
- This invention relates to a method of improving the quality of petroleum hydrocarbons, and more particularly, to improving the. quality of hydrocarbons which have been treated with copper-containing and/or other metal-containing reagents for the removal or conversion of sulfur compounds.
- sweetening operation It is well known to remove sulfur compounds, such as mercaptans, from petroleum hydrocarbons, such as gasoline motor fuels, or to convert such mercaptans into less objectionable compounds by appropriate chemical treatment, generally referred to as a sweetening operation.
- One quite common method of sweetening involves the use of a doctor solution made from sodium hydroxide and lead oxide. Treatment of the sour gasoline with this solution and added sulfur converts the mercaptants to alkyl disulfides.
- the amount of sulfur used must be very carefully controlled since excess sulfur in the gasoline is harmful with respect to corrosiveness, lead susceptibility and inhibitor susceptibility. On the other hand, the use of insufficient sulfur causes lead mercaptides to be left in the fuel.
- an object of my invention to provide an improved method of deactivating metals, such as copper, contained in petroleum hydrocarbons. Another object is to render petroleum hydrocarbons, such as cracked gasoline, more stable to oxidative deterioration catalyzed by metals and to permit more effective use of gasoline antioxidants.
- Still another object is to provide a class of new and effective treating agents for deactivating such metals in petroleum hydrocarbons, such as cracked gasoline.
- the monoesters of citric acid are superior metal deactivators in organic compositions such as gasoline.
- Such monoesters can be employed to deactivate metals such as copper, cobalt, manganese, etc. in organic compositions such as cracked gasoline whereby the product obtained is of greatly improved stability.
- metal deactivators By employing the monoesters of citric acid as metal deactivators, the more economical use of gasoline antioxidants is facilitated, since excessive quantities of antioxidants are required to properly stabilize gasoline containing catalytically-active metals.
- R represents a substituent selected from the group consisting of an alkyl radical containing from 1 to 18 carbon atoms and an aryl radical of the benzene series containing from 6 to 10 carbon atoms.
- suitable radicals include: ethyl, isopropyl, n-butyl, 2-ethylhexyl, cyclohexyl, octadecyl, benzyl, phenyl, tolyl, etc.
- alkyl includes alicyclic radicals. It is generally rather difiicult as a practical matter to obtain the pure monoesters of citric acid. Consequently, this invention also contemplates the employment of citric esters which are mixtures comprising mono-, diand triesters of citric acids even though the pure triesters by themselves have been found to be practically inefiective as metal deactivators.
- a monoester of citric acid is generally required to deactivate any catalytically-active metal that may be present depending on the concentration of metal which exists in the gasoline or other similar organic material being treated. Higher and lower concentrations can also be employed depending upon the circumstances.
- the metal deactivators of this invention can be added alone or in admixture with other additives which are to be incorporated into the material being treated.
- Such other additives include antioxidants, dyes, antiknock compounds, etc.
- the metal deactivators of this invention possess an advantage over known metal deactivators such as N,N'-disalicylidene-1,2-propylenediamine in that they will deactiantioxidant used was N-n-butyl-p-aminophenol.
- the oxygen bomb stability test used to determine the induction periods of the various samples was that described in Industrial and Engineering Chemistry (Ind. Ed.),, vol. 24, p. 1375 (1932).
- Example 1 Methyl citrate deactivating copper by the general formula set forth above can be employed to deactivate the various catalytically-active metals.
- Example 5 M0no lauryl citrate deactivating copper
- the induction period was reduced to 130 minutes.
- the addition of 0.005 weight per cent of an csterification product of citric acid and lauryl alcohol containing a substantial proposition of the mono ester raised the induction period to 360 minutes.
- copper-containing gasoline described in Example 1 was treated with 0.001 weight per cent of another deactivator, mono cyclohexyl citrate.
- the induction period was raised from 145 to 347 minutes.
- Example 3.-M0n0 isopropyl citrate deactivating cobalt This example illustrates the effectiveness of the monoesters of citric acid in deactivating another catalyticallyharmful metal, viz cobalt.
- a Pennsylvania reformed gasoline containing 0.0048 weight per cent of the antioxidant N-n-butyl-p-aminophenol had an induction period of 470 minutes.
- the induction period was reduced to 282 minutes.
- the addition of 0.0005 weight per cent of mono isopropyl citrate to this inhibited, cobaltcontaining fuel raised the induction period to 447 minutes, indicating almost complete deactivation of the metal.
- Example 4.M0.n0 isopropyl citrate deactivating manganese The deactivation of still another catalytically-harmful metal is shown in this example.
- the addition of 1.0 mg. of manganese per liter to the inhibited gasoline described in Example 3 reduced the induction period from 467 to 370 minutes.
- the induction period was raised to 440 minutes indicating substantial improvement in the gasoline stability.
- a motor fuel comprising a cracked gasoline containing a harmful catalytically-active metal reagent intimately admixed with from about 0.0001 to about 0.01 per cent based on the weight of the gasoline of a monoester of citric acid having one of the following formulas:
- R represents a substituent selected from the group consisting of an alkyl radical containing from 1 to 18 carbon atoms and an aryl radical of the benzene series containing from 6 to 10 carbon atoms.
- a motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-isopropyl citrate.
- a motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-n-butyl citrate.
- a motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-cyclohexyl citrate.
- a motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-Z-ethylhexyl citrate.
- a motor fuel as defined in claim 1 wherein the monoester of citric acid is monolauryl citrate.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
Description
limited States Patent O MONO-ESTERS OF CITRIC ACID AS METAL DEACTIVATORS FOR MOTOR FUELS John W. Thompson, Kingsport, Tenn., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 14, 1952, Serial No. 320,607
6 Claims. (Cl. 44-70) This invention relates to a method of improving the quality of petroleum hydrocarbons, and more particularly, to improving the. quality of hydrocarbons which have been treated with copper-containing and/or other metal-containing reagents for the removal or conversion of sulfur compounds.
It is well known to remove sulfur compounds, such as mercaptans, from petroleum hydrocarbons, such as gasoline motor fuels, or to convert such mercaptans into less objectionable compounds by appropriate chemical treatment, generally referred to as a sweetening operation. One quite common method of sweetening involves the use of a doctor solution made from sodium hydroxide and lead oxide. Treatment of the sour gasoline with this solution and added sulfur converts the mercaptants to alkyl disulfides. The amount of sulfur used must be very carefully controlled since excess sulfur in the gasoline is harmful with respect to corrosiveness, lead susceptibility and inhibitor susceptibility. On the other hand, the use of insufficient sulfur causes lead mercaptides to be left in the fuel.
Instead of using the doctor solution method, it has been previously proposed to substitute other sweetening operations employing copper salts for the purpose of removing the sulfur compounds or converting them into less objectionable substances. This operation is widely used for the treatment of petroleum motor fuels, such as gasoline. Frequently in the copper sweetening process various copper compounds may be carried over into the treated gasoline where they are very objectionable since even in trace concentrations they catalyze oxidative deterioration of the treated hydrocarbon. This difliculty is somewhat alleviated through the use of the known antioxidants, although the amount of improvement is not great enough to completely overcome the objections noted above. It is, therefore, desirable to provide some method which would substantially completely remove all heavy metal compounds from the petroleum hydrocarbon, thus allowing the antioxidant to function at its fullest efliciency.
It is, therefore, an object of my invention to provide an improved method of deactivating metals, such as copper, contained in petroleum hydrocarbons. Another object is to render petroleum hydrocarbons, such as cracked gasoline, more stable to oxidative deterioration catalyzed by metals and to permit more effective use of gasoline antioxidants.
Still another object is to provide a class of new and effective treating agents for deactivating such metals in petroleum hydrocarbons, such as cracked gasoline. Other objects will become apparent from a consideration of the following description and examples.
In the prior art the employment of aliphatic esters, such as esters of citric acid, has been suggested for the stabilization of motor fuels containing gum-forming unsaturated compounds (e. g. cracked gasoline) and also for stabilizing mineral wax compositions; however, no partial esters of citric acid have been suggested for such purposes. The prior art discloses the employment of partial esters of citric acid in the stabilizing of edible oils such as various glyceridic oils, e. g. soyabean oil, etc.
According to my invention I have found that the monoesters of citric acid are superior metal deactivators in organic compositions such as gasoline. Such monoesters can be employed to deactivate metals such as copper, cobalt, manganese, etc. in organic compositions such as cracked gasoline whereby the product obtained is of greatly improved stability. By employing the monoesters of citric acid as metal deactivators, the more economical use of gasoline antioxidants is facilitated, since excessive quantities of antioxidants are required to properly stabilize gasoline containing catalytically-active metals.
Thus, I have discovered that the catalytic efiects of metals, such as copper on the oxidative deterioration of organic substances, such as cracked gasoline, can be extensively suppressed by adding to such organic substances a small amount of a monoester of citric acid. These monoesters can be represented by the following general formulas:
and
ore-coon -ooo-R CHr-COOH wherein R represents a substituent selected from the group consisting of an alkyl radical containing from 1 to 18 carbon atoms and an aryl radical of the benzene series containing from 6 to 10 carbon atoms. Examples of suitable radicals that can be employed include: ethyl, isopropyl, n-butyl, 2-ethylhexyl, cyclohexyl, octadecyl, benzyl, phenyl, tolyl, etc. Thus, the term alkyl includes alicyclic radicals. It is generally rather difiicult as a practical matter to obtain the pure monoesters of citric acid. Consequently, this invention also contemplates the employment of citric esters which are mixtures comprising mono-, diand triesters of citric acids even though the pure triesters by themselves have been found to be practically inefiective as metal deactivators.
From about 0.0001 to about 0.1% by weight of a monoester of citric acid is generally required to deactivate any catalytically-active metal that may be present depending on the concentration of metal which exists in the gasoline or other similar organic material being treated. Higher and lower concentrations can also be employed depending upon the circumstances.
The metal deactivators of this invention can be added alone or in admixture with other additives which are to be incorporated into the material being treated. Such other additives include antioxidants, dyes, antiknock compounds, etc. It is advantageous to employ the metal deactivators of this invention in the form of a concentrated solution in a suitable solvent such as a lower aliphatic alcohol (1 to 10 carbon atoms), e. g. isopropanol.
The metal deactivators of this invention possess an advantage over known metal deactivators such as N,N'-disalicylidene-1,2-propylenediamine in that they will deactiantioxidant used was N-n-butyl-p-aminophenol. The oxygen bomb stability test used to determine the induction periods of the various samples was that described in Industrial and Engineering Chemistry (Ind. Ed.),, vol. 24, p. 1375 (1932).
Example 1.-Mno isopropyl citrate deactivating copper by the general formula set forth above can be employed to deactivate the various catalytically-active metals.
Example 5.M0no lauryl citrate deactivating copper A Pennsylvania cracked gasoline containing 0.0048 weight per cent of the antioxidant N-n-butyl-p-aminophenol had an induction period of 555 minutes. Upon 1 addition of 1.0 mg. of copper per liter to this inhibited sample, the induction period was reduced to 130 minutes. However, the addition of 0.005 weight per cent of an csterification product of citric acid and lauryl alcohol containing a substantial proposition of the mono ester raised the induction period to 360 minutes.
TABLE.EFFECTIVENESS OF CITRIC ACID MONESTERS AS METAL DEACTIUVIORS FOR GASOLINE Antioxidant Induction C0nc., Wt. Metal Pres- Deactlvator Period, Test N0. Percent (N- ont, 1 Mg] Deactlvator Compound Cone, Wt. Min. (Oxyn-Butyl-p- Liter Percent gen Bomb aniinophenol) Stab. Test) None None None None 0. 0048 o ..d0 None 522 0.0048 Copper .do None 155 0. 0048 n... Mono isopropyl citrate" 0.001 490 do Mono-n-butyl citrate". 0.001 457 M ono-2-ethylhexyl cltra 0. 001 312 Monocyclohexyl citrate 0.001 347 No None 282 0.0048 d0 0.0005 447 0. 0048 Manganese None. None 370 0.0048 do. Mono isopropyl cltrate.. 0.0005 440 tion period was reduced to 155 minutes, illustrating the harmful effect of copper upon gasoline stability. However, the addition of 0.0010 weight per cent of mono isopropyl citrate to this inhibited, copper-containing fuel gave an induction period of 490 minutes, indicating practically complete restoration of the stability loss due to copper.
Example 2.M0no cycloliexyl citrate deactivating copper The same inhibited, copper-containing gasoline described in Example 1 was treated with 0.001 weight per cent of another deactivator, mono cyclohexyl citrate. The induction period was raised from 145 to 347 minutes.
Example 3.-M0n0 isopropyl citrate deactivating cobalt This example illustrates the effectiveness of the monoesters of citric acid in deactivating another catalyticallyharmful metal, viz cobalt. A Pennsylvania reformed gasoline containing 0.0048 weight per cent of the antioxidant N-n-butyl-p-aminophenol had an induction period of 470 minutes. Upon addition of 1.0 mg. of cobalt/liter to this inhibited sample the induction period was reduced to 282 minutes. However, the addition of 0.0005 weight per cent of mono isopropyl citrate to this inhibited, cobaltcontaining fuel raised the induction period to 447 minutes, indicating almost complete deactivation of the metal.
Example 4.M0.n0 isopropyl citrate deactivating manganese The deactivation of still another catalytically-harmful metal is shown in this example. The addition of 1.0 mg. of manganese per liter to the inhibited gasoline described in Example 3 reduced the induction period from 467 to 370 minutes. Upon the addition of 0.0005 per cent by weight of mono isopropyl citrate to the inhibited fuel containing manganese, the induction period was raised to 440 minutes indicating substantial improvement in the gasoline stability.
In a like manner a number of other citric acid mono esters were found to be effective deactivators for copper in gasoline. The results obtained are shown in the table. It is clearly apparent that any of the monoesters covered What I claim as my invention and desire to secure by LettersPatent of the United States is:
l. A motor fuel comprising a cracked gasoline containing a harmful catalytically-active metal reagent intimately admixed with from about 0.0001 to about 0.01 per cent based on the weight of the gasoline of a monoester of citric acid having one of the following formulas:
CHz-COOR HO2}C OOH and wherein R represents a substituent selected from the group consisting of an alkyl radical containing from 1 to 18 carbon atoms and an aryl radical of the benzene series containing from 6 to 10 carbon atoms.
2. A motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-isopropyl citrate.
3. A motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-n-butyl citrate.
4. A motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-cyclohexyl citrate.
5. A motor fuel as defined in claim 1 wherein the monoester of citric acid is mono-Z-ethylhexyl citrate.
6. A motor fuel as defined in claim 1 wherein the monoester of citric acid is monolauryl citrate.
References Cited in the file of this patent UNITED STATES PATENTS 2,081,407 Minnick May 25, 1937 2,493,717 Christ Jan. 3, 1950 2,523,792 Vahlteich et al. Sept. 26, 1950 2,578,649 Vahlteich et al. Dec. 11, 1951 2,641,539 Thompson et al. June 9, 1953 FOREIGN PATENTS 790,041 France Nov. 12, 1935
Claims (1)
1. A MOTOR FUEL COMPRISING A CRACKED GASOLINE CONTAINING A HARMFUL CATALYTICALLY-ACTIVE METAL REAGENT INTIMATELY ADMIXED WITH FROM ABOUT 0.0001 TO ABOUT 0.01 PER CENT BASED ON THE WEIGHT OF THE GASOLINE OF A MONOESTER OF CITRIC ACID HAVING ONE OF THE FOLLOWING FORMULAS:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US320607A US2747979A (en) | 1952-11-14 | 1952-11-14 | Mono-esters of citric acid as metal deactivators for motor fuels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US320607A US2747979A (en) | 1952-11-14 | 1952-11-14 | Mono-esters of citric acid as metal deactivators for motor fuels |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2747979A true US2747979A (en) | 1956-05-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US320607A Expired - Lifetime US2747979A (en) | 1952-11-14 | 1952-11-14 | Mono-esters of citric acid as metal deactivators for motor fuels |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2811429A (en) * | 1953-08-31 | 1957-10-29 | Eastman Kodak Co | Stabilization of motor fuels |
| US2865723A (en) * | 1953-08-31 | 1958-12-23 | Eastman Kodak Co | Stabilized motor fuels |
| US3017244A (en) * | 1958-05-09 | 1962-01-16 | Texaco Inc | Oxy-thermal process |
| US3068083A (en) * | 1959-07-31 | 1962-12-11 | Socony Mobil Oil Co | Thermally-stable jet combustion fuels |
| US3085069A (en) * | 1959-01-05 | 1963-04-09 | Du Pont | Process for purifying tetraethyllead compositions |
| US3223497A (en) * | 1961-08-31 | 1965-12-14 | Standard Oil Co | Gasoline composition containing a multipurpose additive |
| US3518196A (en) * | 1967-12-18 | 1970-06-30 | Sun Oil Co | Ultraviolet stabilized petroleum hydrocarbons |
| US3948618A (en) * | 1975-06-05 | 1976-04-06 | Ethyl Corporation | Fuel compositions containing glycerides for reducing the plugging of exhaust gas catalysts |
| US4005992A (en) * | 1976-03-08 | 1977-02-01 | Ethyl Corporation | Novel gasoline compositions and additives therefor |
| US4052171A (en) * | 1975-06-05 | 1977-10-04 | Ethyl Corporation | Fuel compositions and additive mixtures containing methanetricarboxylates for reducing exhaust gas catalyst plugging |
| US4866202A (en) * | 1987-03-10 | 1989-09-12 | Lever Brothers Company | Method for synthesizing a salt of a monoester of citric acid |
| WO2010112158A1 (en) * | 2009-03-28 | 2010-10-07 | Citrodiesel Gbr | Citric acid esters as biogens, regenerative fuels and heating materials |
| EP2314661A1 (en) * | 2004-03-11 | 2011-04-27 | Chemtura Corporation | Lubricant and fuel compositions containing hydroxy polycarboxylic acid esters |
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| FR790041A (en) * | 1934-06-30 | 1935-11-12 | Wacker Chemie Gmbh | Method for increasing wetting ability |
| US2081407A (en) * | 1937-05-25 | Drier | ||
| US2493717A (en) * | 1946-05-21 | 1950-01-03 | Gen Aniline & Film Corp | Stabilized iron pentacarbonyl and motor fuel containing the same |
| US2523792A (en) * | 1946-07-30 | 1950-09-26 | Best Foods Inc | Compositions, including esters of citric acid |
| US2578649A (en) * | 1948-02-20 | 1951-12-11 | Best Foods Inc | Glyceridic oil compositions and method of producing same |
| US2641539A (en) * | 1950-04-12 | 1953-06-09 | Universal Oil Prod Co | Preventing discoloration of fuel oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2081407A (en) * | 1937-05-25 | Drier | ||
| FR790041A (en) * | 1934-06-30 | 1935-11-12 | Wacker Chemie Gmbh | Method for increasing wetting ability |
| US2493717A (en) * | 1946-05-21 | 1950-01-03 | Gen Aniline & Film Corp | Stabilized iron pentacarbonyl and motor fuel containing the same |
| US2523792A (en) * | 1946-07-30 | 1950-09-26 | Best Foods Inc | Compositions, including esters of citric acid |
| US2578649A (en) * | 1948-02-20 | 1951-12-11 | Best Foods Inc | Glyceridic oil compositions and method of producing same |
| US2641539A (en) * | 1950-04-12 | 1953-06-09 | Universal Oil Prod Co | Preventing discoloration of fuel oil |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2811429A (en) * | 1953-08-31 | 1957-10-29 | Eastman Kodak Co | Stabilization of motor fuels |
| US2865723A (en) * | 1953-08-31 | 1958-12-23 | Eastman Kodak Co | Stabilized motor fuels |
| US3017244A (en) * | 1958-05-09 | 1962-01-16 | Texaco Inc | Oxy-thermal process |
| US3085069A (en) * | 1959-01-05 | 1963-04-09 | Du Pont | Process for purifying tetraethyllead compositions |
| US3068083A (en) * | 1959-07-31 | 1962-12-11 | Socony Mobil Oil Co | Thermally-stable jet combustion fuels |
| US3223497A (en) * | 1961-08-31 | 1965-12-14 | Standard Oil Co | Gasoline composition containing a multipurpose additive |
| US3518196A (en) * | 1967-12-18 | 1970-06-30 | Sun Oil Co | Ultraviolet stabilized petroleum hydrocarbons |
| US3948618A (en) * | 1975-06-05 | 1976-04-06 | Ethyl Corporation | Fuel compositions containing glycerides for reducing the plugging of exhaust gas catalysts |
| US4052171A (en) * | 1975-06-05 | 1977-10-04 | Ethyl Corporation | Fuel compositions and additive mixtures containing methanetricarboxylates for reducing exhaust gas catalyst plugging |
| US4005992A (en) * | 1976-03-08 | 1977-02-01 | Ethyl Corporation | Novel gasoline compositions and additives therefor |
| US4866202A (en) * | 1987-03-10 | 1989-09-12 | Lever Brothers Company | Method for synthesizing a salt of a monoester of citric acid |
| EP2314661A1 (en) * | 2004-03-11 | 2011-04-27 | Chemtura Corporation | Lubricant and fuel compositions containing hydroxy polycarboxylic acid esters |
| WO2010112158A1 (en) * | 2009-03-28 | 2010-10-07 | Citrodiesel Gbr | Citric acid esters as biogens, regenerative fuels and heating materials |
| US20110232170A1 (en) * | 2009-03-28 | 2011-09-29 | Ecobasis Ag | Citric acid esters as biogenic, regenerative fuels and heating materials |
| CN102378809A (en) * | 2009-03-28 | 2012-03-14 | 埃科巴希斯股份公司 | Citric acid esters as biogens, regenerative fuels and heating materials |
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