EP0924285B1 - Méthode de réduction de l'acidité d'huile brute et de ses fractions - Google Patents

Méthode de réduction de l'acidité d'huile brute et de ses fractions Download PDF

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Publication number
EP0924285B1
EP0924285B1 EP19980123619 EP98123619A EP0924285B1 EP 0924285 B1 EP0924285 B1 EP 0924285B1 EP 19980123619 EP19980123619 EP 19980123619 EP 98123619 A EP98123619 A EP 98123619A EP 0924285 B1 EP0924285 B1 EP 0924285B1
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EP
European Patent Office
Prior art keywords
crude
oil
fractions
crude oil
oxide
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP19980123619
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German (de)
English (en)
Other versions
EP0924285A2 (fr
EP0924285A3 (fr
Inventor
Guido Sartori
David William Savage
Bruce Henry Ballinger
David Craig Dalrymple
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/16—Metal oxides

Definitions

  • the present invention relates to a process for decreasing the acidity and corrosivity of crudes and crude fractions containing petroleum acids.
  • Efforts to minimize naphthenic acid corrosion have included a number of approaches. Examples of such technologies include use of oil soluble reaction products of an alkynediol and a polyalkene polyamine (U.S. Patent 4,647,366), and treatment of a liquid hydrocarbon with a dilute aqueous alkaline solution, specifically, dilute aqueous NaOH or KOH (U.S. Patent 4,199,440).
  • U.S. Patent 4,199,440 notes, however, that the use of aqueous NaOH or KOH solutions that contain higher concentrations of the base form emulsions with the oil, necessitating use of only dilute aqueous base solutions.
  • U.S. Patent 4,199,440 notes, however, that the use of aqueous NaOH or KOH solutions that contain higher concentrations of the base form emulsions with the oil, necessitating use of only dilute aqueous base solutions.
  • Patent 4,300,995 discloses the treatment of carbonous materials particularly coal and its products such as heavy oils, vacuum gas oil, and petroleum residua, having acidic functionalities, with a quaternary base such as tetramethylammonium hydroxide in a liquid (alcohol or water). Additional processes using bases such aqueous alkali hydroxide solutions include those disclosed in Kalichevsky and Kobe, Petroleum Refining With Chemicals , (1956) Ch. 4, and U.S.
  • Certain treatments have been practiced on mineral oil distillates and hydrocarbon oils (e.g., with lime, molten NaOH or KOH, certain highly porous calcined salts of carboxylic acids suspended on carrier media). Whole crude oils were not treated.
  • U.S. Patents 2,795,532 and 2,770,580 disclose processes in which "heavy mineral oil fractions" and "petroleum vapors", respectively are treated, by contacting "flashed vapors" with "liquid alkaline material” containing, inter alia, alkali metal hydroxides and "liquid oil” using mixture of molten NaOH and KOH as the preferred treating agent, with "other alkaline materials, e.g., lime, also employed in minor amounts.”
  • the treatment of whole crudes or fractions boiling at 1050 plus °F (565 + °C) is not disclosed; only vapors and condensed vapors of the 1050 minus °F (565 - °C) fractions, that is, fractions that are vaporizable at the conditions disclosed in '532 are treated.
  • GB 496 779 discloses a method for decreasing the acidity of an acidic crude oil by contacting the oil in the vapour phase at a temperature exceeding 300°C with a catalyst of high porosity and large catalytic surface selected preferably from lithium carbonate and calcium carbonate.
  • U.S. 2,068,979 discloses a method for preventing corrosion in a petroleum still by adding calcium naphthenate to petroleum to react with and scavenge strong free acids such as hydrochloric and sulfuric acids to prevent corrosion in distillation units.
  • strong free acids such as hydrochloric and sulfuric acids
  • the patent makes no claims with respect to naphthenic acids, which would have been formed when the strong acids were converted to salts.
  • Patents have disclosed, inter alia , the addition or formation of calcium carbonate (Cheng et al, U.S. 4,164,472) or magnesium oxide (Cheng et al, US 4,163,728 and 4,179,383, and 4,226,739) dispersions as corrosion inhibitors in fuel products and lubricating oil products, but not in whole or topped crude oil.
  • the present invention provides for a method for decreasing the acidity and corrosivity of an acid-containing, corrosive crude by contacting a starting acid-containing, corrosive crude oil with an effective amount of at least one oxide of manganese to produce a treated crude oil having a decreased acidity and corrosivity.
  • the treated crude contains naphthenate and ketone derivatives of the naphthenic acids. Water may be present in the crude or added or may be absent.
  • the present invention may suitably comprise, consist or consist essentially of the elements disclosed and may be practiced in the absence of an element not disclosed.
  • Naphthenic acid is a generic term used to identify a mixture of organic acids present in petroleum stocks. Naphthenic acids can cause corrosion at temperatures ranging from about 65°C (150°F) to 420°C (790°F). Naphthenic acids are distributed through a wide range of boiling points (i.e., fractions) in acid containing crudes.
  • the present invention provides a method for broadly treating such acids, and most desirably from heavier (higher boiling point) and liquid fractions in which these acids are often concentrated.
  • the naphthenic acids to be removed may be present either alone or in combination with other organic acids, such as phenols.
  • the process of the present invention has utility in processes in which inhibiting or controlling liquid phase corrosion, e.g., of metal surfaces, is desired. More generally, the present invention may be used in applications in which a reduction in the acidity, typically, as evidenced by a decrease in the neutralization number of the acidic crude or a decrease in intensity of the carboxyl band in the infrared spectrum at about 1708 cm -1 of the treated (neutralized) crude, would be beneficial and in which oil-aqueous emulsion formation and large solvent volumes are not desirable. Appearance of a band at 1600 cm -1 indicates the formation of carboxylate groups and at 1715 cm -1 of keto groups from the carboxylic acid groups.
  • the treated crude contains naphthenate and, preferably ketone derivatives of the organic acids.
  • the present invention also provides a method for controlling emulsion formation in acid crudes, by treating a major contributing component of such emulsions, naphthenic and similar organic acids, and by reducing the attendant handling and processing problems.
  • the concentration of acid in the crude oil is typically expressed as an acid neutralization number or total acid number (TAN), which is the number of milligrams of KOH required to neutralize the acidity of one gram of oil. It may be determined according to ASTM D-664.
  • TAN total acid number
  • the decrease in acid content may be determined by a decrease in the neutralization number or in the intensity of the carboxyl band in the infrared spectrum at about 1708 cm -1 . Appearance of a band at 1600 cm -1 indicates the formation of a carboxylate salt and at 1715 cm -1 indicates formation of a keto group from the carboxylic acid groups.
  • Crude oils with total acid numbers of about 1.0 mg KOH/g and lower are considered to be of moderate to low corrosivity (crudes with a total acid number of 0.2 or less generally are considered to be of low corrosivity). Crudes with total acid numbers greater than 1.5 are considered corrosive.
  • the IR analysis is particularly useful in cases in which a decrease in neutralization number is not evident upon treatment with the base as has been found to occur upon treatment with bases weaker than KOH.
  • the crudes that may be used are any naphthenic acid-containing crude oils that are liquid or liquefiable at the temperatures at which the present invention is carried out.
  • the crudes typically have TAN of 0.2 to 10 mg KOH/g.
  • whole crudes means unrefined, undistilled crudes.
  • the contacting is carried out at a temperature between 120 to 300°C, with narrower ranges suitably from about 150°C to 300°C, preferably 200°C to 300°C.
  • Corrosive, acidic crudes i.e., those containing naphthenic acids alone or in combination with other organic acids such as phenols may be treated according to the present invention.
  • the acidic crudes are preferably whole crudes. However, acidic fractions of whole crudes such as topped crudes and other high boiling point fractions also may be treated. Crude oils or crude oil fractions having a boiling point of 650 + °F (343 + °C) 1050 + °F (565 + °C) are treated.
  • the crude is contacted with an effective amount of at least one oxide of manganese at a temperature sufficient to produce a treated crude having a decreased acidity.
  • the oxides include MnO, Mn 2 O 3 and Mn 3 O 4 .
  • the treatment may be carried out in the presence or absence of water as effective. When present water may be added or naturally occurring.
  • Reaction times depend on the temperature and nature of the crude to be treated, its acid content, but typically may be carried out for from less than about 1 hour to about 20 hours to produce a product having a decrease in corrosivity and acid content.
  • the treated crude contains naphthenate salts of the corresponding oxide used in the treatment and more desirably contains ketone derivatives of the naphthenic acids.
  • the material is added as a solid, which also may include a solid-in-liquid slurry, solid-in-water or solid-in-organic liquid slurry or aqueous suspension.
  • the material is added to the acid containing crude in a molar ratio effective to produce a neutralized or partially neutralized (i.e., non-corrosive) crude oil; neutralization may be in whole or partial as desired.
  • Ratios of oxide to total acid of from 0.01:1 moles up to 5:1, preferably 0.25:1 to 2:1 are used.
  • the oxides may be purchased commercially or synthesized using known procedures. In solid form, they may be in the form of a powder or a composite, sized particle or supported on a refractory (ceramic) matrix. Certain of the solids typically occur as crystals of the hydrate.
  • the reaction apparatus was an autoclave with a capacity of 250 ml.
  • the treated oil from Example 1 was distilled to 566°C (1050°F). The distillate was found to have less than 0.08 ppm of manganese. The remaining 36 gms of resid, containing all the manganese oxide, was used to treat another 100 g batch of Bolobo 2/4 crude. As in Example 1, the reaction was carried out in a closed 300 ml autoclave for 24 hours at 300°C. After cooling, the oil was examined by infrared spectroscopy. A band at about 1600 cm -1 , partly superimposed on a band that was already present in the spectrum of untreated Bolobo 2/4, indicated the formation of carboxylate, presumably manganous naphthenate.
  • the reaction apparatus was the same autoclave described in Example 1. 100 g of Gryphon crude, having an acid number of 4.2 mg KOH/g, and 296 mg of Mn 2 O 3 were put into the autoclave and heated at 300°C for 24 hours. After cooling, a sample was centrifuged to separate the solids, then the oil was examined by infrared. A peak at 1715 cm -1 was about 20% as intense as the 1708 cm -1 peak present in untreated Gryphon and due to carboxyl groups. Treatment of the sample with triethylamine did not cause any change in the 1715 cm -1 peak, indicating that it was due to keto groups rather than to residual carboxyl groups.
  • the reaction apparatus was as described in Example 1, except that a non-chilled condenser was attached to the autoclave thus allowing air to enter the reactor and some light ends of the oil to escape.
  • 100 g of Gryphon crude, having an acid number of 4.2 mg KOH/g, and 296 mg of Mn 2 O 3 were put into the autoclave and heated at 300°C for 24 hours. After cooling, a sample was centrifuged to separate the solids, then the oil was examined by infrared spectroscopy. A peak at 1715 cm -1 was about 20% as intense as the starting oil carboxyl groups at 1708 cm -1 . The peak at 1715 cm -1 is attributed to keto groups.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Claims (8)

  1. Procédé de réduction de l'acidité d'un pétrole brut acide ou d'une fraction de pétrole brut acide ayant un point d'ébullition de 343+°C (650+°F) comprenant la mise en contact du pétrole brut acide ou d'une fraction de celui-ci avec 0,01 à 5 moles, par rapport à la teneur en acide du pétrole brut ou de sa fraction de départ, d'au moins un oxyde de manganèse à une température dans la plage de 120 à 300°C.
  2. Procédé selon la revendication 1, dans lequel l'oxyde de manganèse est choisi parmi un ou plusieurs des oxydes suivants : MnO, Mn2O3 et Mn3O4.
  3. Procédé selon la revendication 1 ou 2, dans lequel ladite quantité d'oxyde de manganèse utilisée se situe dans une plage de 0,25 à 2 moles.
  4. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'oxyde de manganèse est utilisé sous forme de suspension solide ou de suspension solide dans liquide.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le pétrole brut de départ a un point d'ébullition de 565+°C (1050+°F).
  6. Procédé selon l'une quelconque des revendications précédentes, dans lequel le pétrole brut ou sa fraction de départ a un indice de neutralisation de 0,2 à 10 mg de KOH/g.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel la mise en contact est effectuée dans la plage de 200 à 300°C.
  8. Utilisation d'au moins un oxyde de manganèse comme agent de réduction d'acidité selon l'une quelconque des revendications 1 à 6.
EP19980123619 1997-12-17 1998-12-10 Méthode de réduction de l'acidité d'huile brute et de ses fractions Expired - Lifetime EP0924285B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US99244997A 1997-12-17 1997-12-17
US992449 1997-12-17

Publications (3)

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EP0924285A2 EP0924285A2 (fr) 1999-06-23
EP0924285A3 EP0924285A3 (fr) 1999-11-17
EP0924285B1 true EP0924285B1 (fr) 2003-10-01

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EP19980123619 Expired - Lifetime EP0924285B1 (fr) 1997-12-17 1998-12-10 Méthode de réduction de l'acidité d'huile brute et de ses fractions

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EP (1) EP0924285B1 (fr)
AU (1) AU745956B2 (fr)
CA (1) CA2252928C (fr)
DE (1) DE69818619T2 (fr)
DK (1) DK0924285T3 (fr)
ES (1) ES2209044T3 (fr)
NO (1) NO985881L (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2946055B1 (fr) 2009-05-29 2012-08-03 Total Raffinage Marketing Procede de reduction de l'acidite naphtenique de charges petrolieres et son utilisation

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB496779A (en) * 1937-01-04 1938-12-06 Bataafsche Petroleum A process for removing naphthenic acids from mineral lubricating oils or lubricating oil fractions
US5389240A (en) * 1993-08-02 1995-02-14 Uop Naphthenic acid removal as an adjunct to liquid hydrocarbon sweetening

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Publication number Publication date
DE69818619T2 (de) 2004-04-29
DE69818619D1 (de) 2003-11-06
CA2252928C (fr) 2005-06-14
ES2209044T3 (es) 2004-06-16
NO985881D0 (no) 1998-12-15
AU9713998A (en) 1999-07-08
NO985881L (no) 1999-06-18
EP0924285A2 (fr) 1999-06-23
DK0924285T3 (da) 2004-02-09
EP0924285A3 (fr) 1999-11-17
CA2252928A1 (fr) 1999-06-17
AU745956B2 (en) 2002-04-11

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