EP0881274B1 - Verfahren zur Verminderung des Sauregehalts von Rohöl - Google Patents

Verfahren zur Verminderung des Sauregehalts von Rohöl Download PDF

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Publication number
EP0881274B1
EP0881274B1 EP19980303913 EP98303913A EP0881274B1 EP 0881274 B1 EP0881274 B1 EP 0881274B1 EP 19980303913 EP19980303913 EP 19980303913 EP 98303913 A EP98303913 A EP 98303913A EP 0881274 B1 EP0881274 B1 EP 0881274B1
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Prior art keywords
oil
crude oil
stream
aqueous base
treated
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EP19980303913
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English (en)
French (fr)
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EP0881274A3 (de
EP0881274A2 (de
Inventor
Ramesh Varadaraj
David William Savage
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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    • 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
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
    • 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
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C10G27/02—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with halogen or compounds generating halogen; Hypochlorous acid or salts thereof
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water

Definitions

  • the present invention relates to a process for decreasing the acidity of a crude oil.
  • U.S. Patent 5,182,013 refers to such recognized approaches as blending of higher naphthenic acid content oil with low naphthenic acid content oil. Additionally, a variety of attempts have been made to address the problem by using corrosion inhibitors for the metal surfaces of equipment exposed to the acids, or by neutralizing and removing the acids from the oil. For example, Kalichevsky and Kobe in Petroleum Refining with Chemicals (1956), Chapter 4, disclose various alkali treatments of crudes and crude fractions. U.S.
  • Patent 4,199,440 which teaches the use of difficult-to-break caustic-in-oil emulsions discloses treatment of a liquid hydrocarbon with a dilute aqueous alkaline solution, specifically dilute aqueous NaOH or KOH.
  • U.S. Patent 4,300,995 discloses the treatment of carbonous material particularly coal and its products, heavy oils, vacuum gas oil, petroleum resids having acidic functionalities with a dilute quaternary base such as tetramethylammonium hydroxide in a liquid (alcohol or water).
  • IR data of the untreated crude show a peak at 3300-3600 cm -1 corresponding to a phenolic hydroxide (Example 6).
  • a process for decreasing the acidity of an acidic crude oil comprising: contacting an acidic crude oil with an effective amount of an aqueous base at conditions of pH and temperature sufficient to form an unstable emulsion of the acidic crude oil in the aqueous base and breaking the emulsion to form a phase containing treated crude oil having a decreased acidity and aqueous phase containing residual base and neutralized acids.
  • Figure 1 describes the unstable oil in water emulsion treatment of the present invention as a standalone process.
  • Figure 2 describes the unstable oil in water emulsion treatment for removal of naphthenic acid from a crude oil at the well head integrated with a representative currently available process.
  • Naphthenic acid is a generic term used to identify a mixture of organic acids present in petroleum stocks. Naphthenic acids may be present either alone or in combination with other organic acids, such as phenols. Naphthenic acids alone or in combination with other organic acids can cause corrosion at temperatures ranging from about 65°C (150°F) to 420°C (790°F).
  • the crudes that may be used are any naphthenic acid-containing whole crude oils that are liquid or liquefiable at the temperatures at which the present invention is carried out.
  • whole crudes means unrefined, non-distilled crudes.
  • the acidic crudes are preferably whole crudes.
  • acidic fractions of whole crudes such as vacuum gas oil also may be treated.
  • An additional benefit of the treatment process is the absence or substantial absence of stable emulsion formation.
  • Stable emulsion formation is undesirable and a particular problem that is encountered during treatment of acidic crudes with aqueous bases.
  • the formation of a stable crude oil-aqueous base emulsion tends to interfere with the efficient separation of the crude oil and aqueous phases and thus with recovery of the treated crude oil.
  • such acids must be removed from the crude oil due to their tendency to encourage stable emulsion formation during processing, especially desalting processes.
  • acidic crudes e.g., those containing naphthenic acids
  • Neutralized acids such as the corresponding naphthenate are present in the second phase or at the interface between the first and second phases.
  • the process produces a treated crude having a decreased acidity and calcium content.
  • the calcium is present as an insoluble, calcium-containing phase that is disposed between the first and second phases when the emulsion is broken.
  • the aqueous phase containing excess base may be recovered and reused in either a batch or continuous process to contact additional untreated crude, typically until the pH of the recovered aqueous phase reaches a pH of 8.0.
  • the aqueous phase is not completely neutralized and excess base is present in the recovered aqueous base.
  • the aqueous base is suitably an aqueous Group IA or IIA hydroxide, preferably NaOH or KOH solution, more preferably NaOH, having a pH of at least 8, preferably 8 to 12.
  • aqueous Group IA or IIA hydroxide preferably NaOH or KOH solution, more preferably NaOH, having a pH of at least 8, preferably 8 to 12.
  • An unstable emulsion is formed by adding the acidic crude oil with only mild agitation to the aqueous base in a sufficient ratio to produce a dispersion of oil in a continuous aqueous base phase.
  • the crude oil should be added to the aqueous base rather than the aqueous base being added to the crude oil, in order to minimize formation of a stable aqueous base-in-oil emulsion.
  • a ratio of 1:3 to 1:15, preferably 1:3 to 1:4 of oil to aqueous base is used based on the weight of oil and water.
  • a stable emulsion will form if the ratio of oil to aqueous base is 1:1 or less.
  • the weight percent of base in water ranges from 0.5 to 3.0%.
  • Droplet size of from 10-50 microns preferably 20-50 microns is typically needed.
  • Contacting of the crude oil and aqueous phase should be carried out for a period of time sufficient to disperse the oil in the aqueous phase preferably to cause at least 50% by weight, more preferably at least 80%, most preferably 90% of the oil in the aqueous phase.
  • the contacting of the crude oil and aqueous base solution to form the unstable emulsion is carried out at temperature typically from about 10°C to 40°C. At temperatures of greater than 40°C the probability of forming a stable emulsion increases.
  • Contacting times depend on the nature of the crude to be treated, its acid content, and the amount and type of aqueous base added, but typically may be carried out for from about 2 minutes to about 2 hours. Similarly, time needed to coalesce or destabilize the emulsion will vary but typically 1-2 minutes is a minimum. Oil type, particle size and distribution of oil droplets affects coalescence/destabilization rates. Gravity or an electrostatic field may be applied to facilitate demulsification. Destabilizing or demulsifying additives or agents are not required, but may be used to enhance the rate of emulsion breaking.
  • non-ionic surfactant preferably of a straight chain ethoxylated alcohol having a chain length of from 12 to 18 carbon atoms and from 10 to 50 ethoxy groups typically in an amount of less than 0.001 wt% based on weight of crude oil to enhance formation of the unstable emulsion.
  • the emulsion may be broken by any suitable method, preferably by gravity coalescence to generate a treated crude having a reduced acidity and an aqueous phase containing napthenate salts.
  • bases and surfactants suitable for use in the process may be purchased commercially or synthesized using known procedures.
  • the concentration of acid in the crude oil is typically expressed as an acid neutralization number or acid number, 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.
  • Any acidic crude may be treated according to the present invention, for example, crudes having an acid neutralization number of from 0.5 to 10 mg KOH/g oil.
  • 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 .
  • Whole crude oils with acid numbers of about 1.0 and lower are considered to be of moderate to low corrosivity. Crudes with acid numbers greater than 1.5 are considered corrosive. Acidic crudes having free carboxyl groups may be effectively treated using the process of the present invention.
  • 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 of an acidic whole crude would be beneficial.
  • the process is especially beneficial for treatment to decrease acidity and calcium content of acidic crude oils at the wellhead.
  • Such crudes typically contain impurities such as naturally occurring or coproduced water and gases.
  • a full well stream containing whole acidic crude oil, water and gases is passed via line 1 to a separator 3, and separated into a gas stream, which is removed via line 2, a water stream containing trace amounts of oil which is removed via line 4 and combined with base, typically aqueous, from line 6 prior to entering contactor 7, and an oil stream containing trace amounts of water which is passed via line 5 to contactor 7.
  • the upper water and base stream from line 4 and 6 and lower oil stream from line 5 are contacted in contactor 7 to form an unstable oil in aqueous base emulsion.
  • Treated oil containing residual water is drawn off overhead from contactor 7 via line 5a and passed to separator 8 to separate the treated oil from residual aqueous base.
  • the lower phase of aqueous base containing residual treated oil is drawn off below via line 4a and passed to separator 9 from which aqueous base is recovered and passed out via line 10 and may be recycled to line 6 or disposed of, and residual treated oil is passed via line 9a to stabilizer tower 12.
  • separator 8 treated oil is removed via line 8b to stabilizer tower 12 while aqueous base is removed via line 8a to separator 9.
  • gases and volatiles are removed through line 13 and treated oil via line 11.
  • the new contactor is represented by the block 7 and the lines connecting it to a typical current process.
  • the feeds to contactor 7 are water via line 4 and the oil via line 5.
  • the aqueous base from lines 4 and 6 and oil from line 5 are mixed so as to form the unstable oil-in-caustic emulsion as described with respect to Figure 1, and after a sufficient mixing time, the phases are allowed to separate.
  • the separated aqueous base-containing residual oil phase is passed via line 4a to separator 9, and the separated oil phase to separator 8.
  • Valves V1 and V2 are provided to allow operation of the crude oil treatment process either in whole or in part with, or without the portions of the process associated with forming the unstable emulsion and separating the resulting products (contactor 7 and lines connected thereto) described in Figure 1.
  • the reference numerals in Figure 2 correspond to the same numerals in Figure 1.
  • Bolobo 2/4 (Chad crude oil) was added to 80 ml of 1.5 wt% NaOH solution in a separatory funnel.
  • the oil/water mixture was shaken gently on a wrist shaker for 20 minutes. It was determined by droplet size measurements using a Coulter Multisizer 11 instrument that greater than 90% of the crude oil was dispersed as an oil-in-water emulsion. After contacting for 20 minutes, the shaker was stopped and the emulsion allowed to stand. In 10 minutes the emulsion destabilized and a yellowish lower aqueous phase separated out. The aqueous phase pH of 8.0 and the treated oil were separated. The aqueous phase was reused by repeating the above experiment (Example 2) with addition of a fresh batch of 20g of Bolobo 2/4 crude. Two treated crude oil samples were generated from the experiment:
  • Example 1 The procedure of Example 1 was repeated using ammonium hydroxide instead of sodium hydroxide. No reduction in acidity or extraction of acid into the aqueous phase was observed.
  • Example 1 The procedure of Example 1 was repeated using tetrabutyl ammonium hydroxide instead of sodium hydroxide. A stable unbreakable emulsion resulted. The treated crude could not be separated from the aqueous phase.

Claims (10)

  1. Verfahren zur Verringerung der Acidität eines sauren Rohöls, bei dem:
    (a) eine instabile Emulsion des sauren Rohöls in einer wässrigen Base gebildet wird, indem das Rohöl mit einer wirksamen Menge der wässrigen Base bei pH- und Temperaturbedingungen gemischt wird, die geeignet sind, eine instabile Emulsion zu ergeben,
    (b) die instabile Emulsion gebrochen wird, um eine erste Phase, die behandeltes Rohöl mit einer verringerten Acidität enthält, und eine zweite wässrige Phase herzustellen, die restliche Base und neutralisierte Säuren enthält.
  2. Verfahren nach Anspruch 1, bei dem das saure Rohöl ein Calcium enthaltendes saures Rohöl ist.
  3. Verfahren nach Anspruch 2, bei dem das Brechen der Emulsion eine dritte, Calciumverbindungen enthaltende Phase erzeugt, die sich zwischen der ersten und zweiten Phase befindet und von diesen abtrennbar ist.
  4. Verfahren nach Anspruch 2 oder 3 zur Verringerung der Acidität und des Calciumgehalts eines Calcium enthaltenden sauren Rohöls mit Wasserverunreinigungen, bei dem
    (a) das Rohöl in einen ersten Strom, der hauptsächlich Wasser und Spurenmengen des Rohöls enthält, und einen zweiten Strom, der hauptsächlich Rohöl und Spurenmengen an Wasser enthält, getrennt wird;
    (b) der erste Strom mit wässriger Base kombiniert wird;
    (c) der erste Strom mit wässriger Base aus (b) und der zweite Strom aus (a) im Gegenstrom kontaktiert werden, um eine instabile Öl-in-wässriger-Base-Emulsion zu ergeben;
    (d) eine untere Phase, die hauptsächlich wässrige Base und restliches behandeltes Öl enthält, und eine obere Phase, die hauptsächlich behandeltes Öl und restliche wässrige Base enthält, gewonnen werden,
    (e) die obere Phase aus Stufe (d) in einen behandelten Ölstrom, der restliches Wasser enthält, und einen wässrigen Basenstrom, der restliches behandeltes Öl enthält, aufgetrennt wird;
    (f) die untere Phase aus Stufe (d) und der wässrige Basenstrom aus Stufe (e) in einen Separator geleitet werden, um einen wässrigen Basestrom und einen behandelten Ölstrom zu gewinnen;
    (g) der behandelte Ölstrom aus Stufe (e) und der behandelte Ölstrom aus Stufe (f) in einen Stabilisatorturm geleitet werden; und
    (h) der behandelte Ölstrom entgast und gewonnen wird.
  5. Verfahren nach einem vorhergehenden Anspruch, bei dem das saure Rohöl in der wässrigen Emulsion eine Tröpfchengröße von 10 bis 50 µm hat.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das saure Rohöl naphthenische Säuren enthält.
  7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Base in einer Menge von etwa 0,5 bis 3 Gew.-% in Wasser vorliegt, wenn das Rohöl zugegeben wird.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem ein Gewichtsverhältnis von saurem Rohöl zu wässriger Base von 1 : 3 bis 1 : 15 zur Herstellung der instabilen Emulsion verwendet wird.
  9. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Base ausgewählt ist aus Gruppe IA und IIA Hydroxiden, bevorzugt NaOH oder KOH.
  10. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die wässrige Base außerdem ein nichtionisches ethoxyliertes Alkoholtensid mit 10 bis 50 Ethoxygruppen und einer Kettenlänge von 12 bis 18 Kohlenstoffatomen enthält.
EP19980303913 1997-05-30 1998-05-18 Verfahren zur Verminderung des Sauregehalts von Rohöl Expired - Lifetime EP0881274B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86646297A 1997-05-30 1997-05-30
US866462 1997-05-30

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EP0881274A2 EP0881274A2 (de) 1998-12-02
EP0881274A3 EP0881274A3 (de) 1999-02-10
EP0881274B1 true EP0881274B1 (de) 2003-08-13

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EP19980303913 Expired - Lifetime EP0881274B1 (de) 1997-05-30 1998-05-18 Verfahren zur Verminderung des Sauregehalts von Rohöl

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EP (1) EP0881274B1 (de)
AU (1) AU740689B2 (de)
BR (1) BR9801716A (de)
DE (1) DE69817080T2 (de)
ID (1) ID20373A (de)
MY (1) MY121296A (de)
NO (1) NO316075B1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6030523A (en) * 1997-05-30 2000-02-29 Exxon Research And Engineering Co. Process for neutralization of petroleum acids (LAW810)
GB9912842D0 (en) * 1999-06-02 1999-08-04 Bp Exploration Operating Process for reducing the acidity of oil
US6454936B1 (en) * 2001-03-09 2002-09-24 Exxonmobil Research And Engineering Company Removal of acids from oils
GB2462956B (en) 2007-06-20 2011-06-29 Akzo Nobel Nv A method for preventing the formation of calcium carboxylate deposits in the dewatering process for crude oil/water streams
MY164238A (en) 2012-07-27 2017-11-30 Petroliam Nasional Berhad (Petronas) A process of desalting crude oil
US9162944B2 (en) 2013-04-06 2015-10-20 Agilyx Corporation Systems and methods for conditioning synthetic crude oil
CN110407686B (zh) * 2019-06-27 2022-03-04 五矿（北京）稀土研究院有限公司 一种从混合有机物中分离环烷酸的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2229995A (en) * 1939-05-05 1941-01-28 Shell Dev Process for removing acid components from hydrocarbon distillates
US2662062A (en) * 1950-08-26 1953-12-08 Standard Oil Dev Co Resolving emulsions
US3806437A (en) * 1973-03-22 1974-04-23 Petrolite Corp Treatment of petroleum distillates containing naphthenic acids
FR2388037A1 (fr) * 1977-04-20 1978-11-17 Raffinage Cie Francaise Procede perfectionne de dessalage du petrole brut et dispositifs de mise en oeuvre dudit procede
US4199440A (en) * 1977-05-05 1980-04-22 Uop Inc. Trace acid removal in the pretreatment of petroleum distillate
GB8431013D0 (en) * 1984-12-07 1985-01-16 British Petroleum Co Plc Desalting crude oil
JP3839849B2 (ja) * 1995-08-25 2006-11-01 エクソンモービル リサーチ アンド エンジニアリング カンパニー 原油の酸含有量及び腐食性の低下方法

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DE69817080D1 (de) 2003-09-18
AU6906298A (en) 1998-12-03
EP0881274A3 (de) 1999-02-10
NO982388L (no) 1998-12-01
BR9801716A (pt) 1999-12-21
MY121296A (en) 2006-01-28
NO982388D0 (no) 1998-05-26
NO316075B1 (no) 2003-12-08
ID20373A (id) 1998-12-03
DE69817080T2 (de) 2004-06-17
AU740689B2 (en) 2001-11-08
EP0881274A2 (de) 1998-12-02

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