WO2011159764A1 - Inhibition de la fissuration par corrosion sous contrainte d'un métal exposé à des concentrations modérées à élevées d'éthanol - Google Patents

Inhibition de la fissuration par corrosion sous contrainte d'un métal exposé à des concentrations modérées à élevées d'éthanol Download PDF

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Publication number
WO2011159764A1
WO2011159764A1 PCT/US2011/040452 US2011040452W WO2011159764A1 WO 2011159764 A1 WO2011159764 A1 WO 2011159764A1 US 2011040452 W US2011040452 W US 2011040452W WO 2011159764 A1 WO2011159764 A1 WO 2011159764A1
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WO
WIPO (PCT)
Prior art keywords
ethanol
acid
blend
fuel
corrosion inhibitor
Prior art date
Application number
PCT/US2011/040452
Other languages
English (en)
Inventor
Tracey Jackson
Rusty Strong
Original Assignee
Champion Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Champion Technologies, Inc. filed Critical Champion Technologies, Inc.
Publication of WO2011159764A1 publication Critical patent/WO2011159764A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/12—Oxygen-containing compounds
    • C23F11/124—Carboxylic acids
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • 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
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C10L1/1883—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom polycarboxylic acid
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation

Definitions

  • the present invention relates to the use of chemical additives to inhibit corrosion of a metal that is exposed to moderate to high concentrations of ethanol, such as in certain blends of transportation fuel and ethanol.
  • Transportation fuels such as gasoline and diesel
  • gasoline and diesel are liquid hydrocarbon mixtures that are used in internal combustion engines. These transportation fuels are produced from crude oil in an oil refinery and distributed to gasoline stations where they are sold to retail consumers in smaller quantities.
  • the oil refineries are typically located where large amounts of crude oil can be easily delivered, such as near a coastline where the crude oil is delivered by large ships.
  • gasoline stations that sell both gasoline and diesel are located throughout the regions where fuel is needed for operating automobiles, farm equipment, and other devices having internal combustion engines.
  • gasoline and diesel fuel may be transported from an oil refinery to gasoline stations by truck.
  • gasoline for example, may be transported from an oil refinery through a pipeline to a regional distribution center before being taken to proximate gasoline stations by truck.
  • One embodiment of the present invention provides a method for inhibiting corrosion of metal exposed to a blend of fuel and ethanol.
  • the method comprises adding an effective stress corrosion cracking inhibiting amount of a corrosion inhibitor into the blend of fuel and ethanol that contacts the metal, wherein the corrosion inhibitor is an organic acid selected from citric acid, ascorbic acid, succinic acid, pyruvic acid, maleic acid, oxaloacetic acid, oxalosuccinic acid, ketoglutaric acid, isocitric acid, malic acid, aconitic acid, fumaric acid, isomers of these organic acids, and a combination thereof.
  • the corrosion inhibitor is an organic acid selected from citric acid, ascorbic acid, succinic acid, pyruvic acid, maleic acid, oxaloacetic acid, oxalosuccinic acid, ketoglutaric acid, isocitric acid, malic acid, aconitic acid, fumaric acid, isomers of these organic acids, and a combination thereof.
  • Another embodiment of the present invention provides a further method for inhibiting corrosion of metal exposed to a blend of fuel and ethanol.
  • the method comprises adding an effective stress corrosion cracking inhibiting amount of a corrosion inhibitor into the blend of fuel and ethanol that contacts the metal, wherein the corrosion inhibitor is an organic acid having one or more functional groups selected from carboxylic acids, alkene bonds, hydroxyl groups, and combinations thereof.
  • the present invention provides a method for inhibiting corrosion of metal in a pipeline containing a blend of gasoline and ethanol.
  • the method comprises adding an effective corrosion inhibiting amount of a corrosion inhibitor into a blend of gasoline and ethanol flowing through a pipeline, wherein the corrosion inhibitor is an organic acid selected from citric acid, ascorbic acid, succinic acid, pyruvic acid, maleic acid, oxaloacetic acid, oxalosuccinic acid, ketoglutaric acid, isocitric acid, malic acid, aconitic acid, fumaric acid, isomers of these organic acids, and a combination thereof.
  • the corrosion inhibitor is an organic acid selected from citric acid, ascorbic acid, succinic acid, pyruvic acid, maleic acid, oxaloacetic acid, oxalosuccinic acid, ketoglutaric acid, isocitric acid, malic acid, aconitic acid, fumaric acid, isomers of these organic acids, and a combination thereof.
  • the present invention may be used with any ethanol concentration, but the corrosion inhibitors are effective where the ethanol concentration in the blend of fuel and ethanol is greater than ten percent, greater than fifteen percent, greater than twenty-five percent, or even greater than 95 percent.
  • the corrosion inhibitors are effective for inhibiting stress corrosion cracking of metal exposed to high concentrations of ethanol, such as in the fuel mixture known as E85 containing up to 85% ethanol and gasoline.
  • the selected organic acid is ammoniated.
  • the organic acid may be mixed with ammonium hydroxide in substantially stoichiometric amounts such that the organic acid is present as the ammonium salt of the organic acid.
  • the corrosion inhibitor is added into the blend of fuel and ethanol in an amount providing between 10 and 1000 ppm of the corrosion inhibitor based on the ethanol content of the blend. More specifically, the corrosion inhibitor may be added into the blend in an amount providing between 100 and 600 ppm of the corrosion inhibitor based on the ethanol content of the blend.
  • the corrosion inhibitors are equally effective regardless of whether they are added before or after the blending of the ethanol and fuel.
  • the corrosion inhibitor is optionally added as a solution including a solvent selected from water, methanol, and combinations thereof.
  • a solvent selected from water, methanol, and combinations thereof.
  • the solvent delivery system used with the corrosion inhibitor is not believed to play any role in the performance of the corrosion inhibitor in inhibiting stress corrosion cracking, but should not interfere with the ultimate use of the fuel blend.
  • the method includes flowing the blend of fuel and ethanol through a pipeline including metal exposed to the blend of fuel and ethanol. Accordingly, the corrosion inhibitor is added into the flowing blend of fuel and ethanol at a plurality of injection points spaced apart along the length of a pipeline. Adding the corrosion inhibitor in this manner preferably enables a sufficient concentration of the corrosion inhibitor throughout the length of the pipeline.
  • the method may include storing the blend of fuel and ethanol in a storage tank including metal exposed to the blend of fuel and ethanol.
  • the foregoing corrosion inhibitors are used in combination with one or more other corrosion inhibitors. It is believed that the corrosion inhibitors of the present invention are effective for inhibiting ethanol-induced stress corrosion cracking, whereas conventional corrosion inhibitors may also be used to inhibit corrosion caused by other components flowing in the pipe and/or corrosion of other types or mechanisms. For example, 500 ppm citric acid may be added into the blend of ethanol and fuel to inhibit stress corrosion cracking, while one or more conventional corrosion inhibitors may also be added into the blend of ethanol and gasoline to inhibit general corrosion or pitting.
  • a conventional corrosion inhibitor may include a sulfur-containing functional group (such as a mercapto or thiol) or a quaternary amine functional group.
  • the conventional corrosion inhibitor may be an imidazoline corrosion inhibitor.
  • the conventional corrosion inhibitor may be selected from dimer acids, trimer acids, derivatives of succinic anhydride, and combinations thereof.
  • the conventional corrosion inhibitors may be used in one of the foregoing methods further comprising the step of adding an effective general corrosion inhibiting amount of a conventional corrosion inhibitor into the blend of fuel and ethanol.
  • SSR slow strain rate
  • crack growth tests were performed on base metal specimens machined from one X-60 line pipe steel to illustrate the effectiveness of various inhibitors at preventing ethanol stress corrosion cracking (SCC).
  • the testing was performed with un-notched specimens having a gage length of 25 mm (1 inch) and a gage diameter of 3.2 mm (0.125 inches).
  • a displacement rate of 1 x 10 "6 inches/sec was used, which produced a strain rate of 1 x 10 "6 sec "1 .
  • the SSR tests were performed in stainless steel test cells with a total volume of 400 mL, where the volume was filled with 350 mL of solution leaving a vapor space of 50 mL.
  • the tests were performed using a simulated fuel grade ethanol (SFGE) containing 5 ppm chloride (CI).
  • SFGE simulated fuel grade ethanol
  • CI ppm chloride
  • the specimens were tested under freely corroding conditions and the corrosion potential was monitored in each test using an Ag/AgCl/EtOH reference electrode. Based on independent measurements of chloride leakage rate from the reference electrode, it was estimated that the chloride concentration in the test cell increased by about 1 ppm during the course of the SSR tests.
  • a piece of rusted pipe steel was placed in the test cell and galvanically connected to the test specimen to more closely simulate the native corrosion potential of a mill scaled/rusted pipe wall. The rusted steel to specimen area ratio was approximately 5 to 1.
  • the specimen and rusted steel piece were electrically isolated from the specimen grips and test cell in the SSR test machine.
  • the tests were performed at room temperature and the cell was actively sparged with breathing air at a flow rate of approximately 4 mL/minute.
  • Ethanol bubbler traps were used on the inlet and outlet to the test cell to remove/exclude any moisture. Post-test analysis was not performed on the test solutions, but extensive previous water analyses of test solutions from the SSR tests indicated that there was negligible pick-up of water in the tests.
  • Table 1 summarizes the results of the SSR tests.
  • the first column in the table identifies the conditions to which the specimen was exposed, including air, FGE, SFGE and various inhibitors.
  • the second column in the table is the total time to failure in the SSR test, in hours.
  • the third column in the table is the reduction in area of the cross section of the specimen, in percent. In general, less reduction in area occurs in the smooth tensile specimens that exhibit cracking.
  • the fourth column in the table is the maximum stress sustained by the specimen, the ultimate tensile strength (UTS), which is the maximum load divided by the initial cross sectional area.
  • UTS ultimate tensile strength
  • the fifth column in Table 1 is the time-to-failure ratio, which is the time to failure for each test divided by the average time to failure for the duplicate air tests of specimens of the same material.
  • the sixth column in the table is the reduction in area ratio (for un-notched specimens), which is the reduction in area for each test specimen divided by the average reduction in area for the air tests.
  • the seventh column in the table is the UTS ratio, which is the UTS for each test specimen divided by the average UTS for the air tests.
  • the eighth column in Table 1 is the crack depth, in micrometers, measured on the fracture surface in the SEM.
  • the depth of the second deepest thumbnail crack on the fracture surface of each specimen is recorded, since in some cases the deepest crack was not representative of the other cracks found on the fracture surface.
  • the ninth column in the table is the pseudo-crack growth rate, in mm/s, calculated by dividing the crack depth by the time to failure. No change ("-") in columns eight and nine indicates that no cracking was found in the specimen.
  • the time to failure, reduction in area, UTS, ratios of these parameters to the air tests, crack depth, and crack growth rate all provide indications of the severity of SCC that occurred in the specimen.
  • the time to failure ratio, reduction in area ratio, and UTS ratios are preferable to the underlying parameters since they more easily indicate cracking severity. The smaller the value of the ratio relative to one, the more severe the cracking.
  • the tenth column in Table 1 is the average corrosion potential. In each test, corrosion potential readings were recorded every minute using a data acquisition system. The potential data for each test were averaged and the results are shown in Column 10.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Emergency Medicine (AREA)
  • Combustion & Propulsion (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Fuel-Injection Apparatus (AREA)

Abstract

Selon la présente invention, une quantité inhibitrice efficace de la fissuration par corrosion sous contrainte d'un inhibiteur de corrosion est ajoutée à un mélange de carburant et d'éthanol qui entre en contact avec un métal, l'inhibiteur de corrosion étant un acide organique choisi parmi l'acide citrique, l'acide ascorbique, l'acide succinique, l'acide pyruvique, l'acide maléique, l'acide oxaloacétique, l'acide oxalosuccinique, l'acide cétoglutarique, l'acide isocitrique, l'acide malique, l'acide aconitique, l'acide fumarique, les isomères de ces acides organiques, et leur association. Par exemple, les inhibiteurs de corrosion inhibent la fissuration par corrosion sous contrainte d'un tuyau métallique de qualité canalisation à des concentrations en éthanol supérieures à quinze pour cent. Dans un mode de réalisation, l'inhibiteur de corrosion est ajouté à un mélange de carburant et d'éthanol s'écoulant dans une canalisation en une pluralité de points d'injection espacés sur la longueur de la canalisation. Selon une option, l'inhibiteur de corrosion est ammoniaqué pour former le sel d'ammonium de l'acide organique. Selon une autre option, les inhibiteurs de corrosion précédents sont utilisés en association avec un ou plusieurs inhibiteurs de corrosion classiques dans une quantité qui est efficace pour inhiber la corrosion générale.
PCT/US2011/040452 2010-06-15 2011-06-15 Inhibition de la fissuration par corrosion sous contrainte d'un métal exposé à des concentrations modérées à élevées d'éthanol WO2011159764A1 (fr)

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US61/355,028 2010-06-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD4245C1 (ro) * 2012-04-19 2014-02-28 Институт Химии Академии Наук Молдовы Inhibitor de coroziune a oţelului în apă
MD4310C1 (ro) * 2013-07-17 2015-06-30 Институт Химии Академии Наук Молдовы Inhibitor de coroziune a oţelului în apă

Families Citing this family (2)

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US9732430B2 (en) 2013-10-24 2017-08-15 Baker Hughes Incorporated Chemical inhibition of pitting corrosion in methanolic solutions containing an organic halide
GB202200031D0 (en) * 2022-01-04 2022-02-16 Innospec Ltd Corrosion inhibitor

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US4242099A (en) * 1979-02-09 1980-12-30 Ethyl Corporation Fuel additive for diesel fuels
US4440545A (en) * 1981-11-02 1984-04-03 Ethyl Corporation Gasohol having corrosion inhibiting properties
US4508540A (en) * 1981-11-02 1985-04-02 Ethyl Corporation Alcohol based fuels
US4521219A (en) * 1981-11-02 1985-06-04 Ethyl Corporation Alcohol based fuels containing corrosion inhibitors
US5356546A (en) * 1992-04-16 1994-10-18 The Lubrizol Corporation Metal salts useful as additives for fuels and lubricants
WO1999031203A1 (fr) * 1997-12-12 1999-06-24 Caterpillar Inc. Melange aqueux de carburant a pouvoir calorifique constant et procede de preparation dudit carburant
US20070113467A1 (en) * 2005-11-23 2007-05-24 Novus International Inc. Biodiesel fuel compositions having increased oxidative stability
EP1967567A2 (fr) * 2007-02-22 2008-09-10 Afton Chemical Corporation Procédés et compositions de réduction de dépôts dans des moteurs à combustion de carburants contenant de l'alcool
EP1967566A1 (fr) * 2007-03-08 2008-09-10 Afton Chemical Corporation Procédés et compositions de réduction de corrosion et d'augmentation de la durabilité de moteur dans des moteurs consommant des carburants à base d'alcool
WO2010042378A1 (fr) * 2008-10-10 2010-04-15 The Lubrizol Corporation Additifs pour carburants permettant de réduire l'arrachement de métal

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2715572A (en) * 1951-09-13 1955-08-16 Karl F Hager Camphoric acid salts as inhibitors for water soluble fuels
US4242099A (en) * 1979-02-09 1980-12-30 Ethyl Corporation Fuel additive for diesel fuels
US4440545A (en) * 1981-11-02 1984-04-03 Ethyl Corporation Gasohol having corrosion inhibiting properties
US4508540A (en) * 1981-11-02 1985-04-02 Ethyl Corporation Alcohol based fuels
US4521219A (en) * 1981-11-02 1985-06-04 Ethyl Corporation Alcohol based fuels containing corrosion inhibitors
US5356546A (en) * 1992-04-16 1994-10-18 The Lubrizol Corporation Metal salts useful as additives for fuels and lubricants
WO1999031203A1 (fr) * 1997-12-12 1999-06-24 Caterpillar Inc. Melange aqueux de carburant a pouvoir calorifique constant et procede de preparation dudit carburant
US20070113467A1 (en) * 2005-11-23 2007-05-24 Novus International Inc. Biodiesel fuel compositions having increased oxidative stability
EP1967567A2 (fr) * 2007-02-22 2008-09-10 Afton Chemical Corporation Procédés et compositions de réduction de dépôts dans des moteurs à combustion de carburants contenant de l'alcool
EP1967566A1 (fr) * 2007-03-08 2008-09-10 Afton Chemical Corporation Procédés et compositions de réduction de corrosion et d'augmentation de la durabilité de moteur dans des moteurs consommant des carburants à base d'alcool
WO2010042378A1 (fr) * 2008-10-10 2010-04-15 The Lubrizol Corporation Additifs pour carburants permettant de réduire l'arrachement de métal

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD4245C1 (ro) * 2012-04-19 2014-02-28 Институт Химии Академии Наук Молдовы Inhibitor de coroziune a oţelului în apă
MD4310C1 (ro) * 2013-07-17 2015-06-30 Институт Химии Академии Наук Молдовы Inhibitor de coroziune a oţelului în apă

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