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US20030150779A1 - Process for removing metal ions from crude oil - Google Patents

Process for removing metal ions from crude oil Download PDF

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Publication number
US20030150779A1
US20030150779A1 US10/296,598 US29659802A US2003150779A1 US 20030150779 A1 US20030150779 A1 US 20030150779A1 US 29659802 A US29659802 A US 29659802A US 2003150779 A1 US2003150779 A1 US 2003150779A1
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US
United States
Prior art keywords
ether
glycol mono
crude oil
metal
solvent
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.)
Abandoned
Application number
US10/296,598
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English (en)
Inventor
Ian Collins
Simon Duncum
Christopher Osborne
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Exploration Operating Co Ltd
Original Assignee
BP Exploration Operating Co Ltd
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 BP Exploration Operating Co Ltd filed Critical BP Exploration Operating Co Ltd
Assigned to BP EXPLORATION OPERATING COMPANY LIMITED reassignment BP EXPLORATION OPERATING COMPANY LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUNCUM, SIMON NEIL, COLLINS, IAN RALPH, OSBOURNE, CHRISTOPHER GEORGE
Publication of US20030150779A1 publication Critical patent/US20030150779A1/en
Abandoned legal-status Critical Current

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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
    • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12—Organic compounds only
    • C10G21/16—Oxygen-containing compounds

Definitions

  • the present invention relates to a process for removing metal ions from crude oil.
  • Crude oil and its distillates often contain metal ion impurities.
  • impurities include metal ions from Group IA and IIA of the Periodic Table, such as sodium, potassium, calcium and magnesium. These impurities often find their way into the oil when the oil is deacidified, as metal oxides, hydroxides and/or carbonates are routinely employed as neutralising agents.
  • Metal ions in the oil can cause fouling problems, particularly, in refinery operations. This is because in such operations, high temperatures in excess of 200° C. are encountered, causing the metals to deposit on the refinery equipment. For this reason, it is desirable to remove metal ions from the oil.
  • WO 98/14402 describes a process for removing +2 ionic charged metals from a petroleum feed. The process involves contacting the feed with a resin that includes carboxyl, sulphonic and/or phosphonic groups.
  • the present invention provides a process for removing metal ions from crude oil comprising
  • the contacting step is carried out in the presence of water.
  • crude oil is intended to cover whole crudes as well as crude oil distillates. Preferably, however, the process is carried out on whole crude oils.
  • the non-ionic amphiphilic solvent may be an alcohol.
  • the solvent is a polyol, such as an alcyltriglycol ether.
  • the alkyl group of the alkyltriglycol ether may be straight or branched chain and suitably has 3-6 carbon atoms, preferably 3-5 carbon atoms. More preferably, the allyl group in the alkyltrigycol ether has 4 carbon atoms and is especially n-butyltriglycol ether (also known as triethylene glycol mono-n-butyl ether).
  • glycol ethers include ethylene glycol mono ethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-2-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-iso-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-iso-butyl ether, diethylene glycol mono-2-butyl ether, diethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-pentyl ether, diethylene glycol mono-2-methylbutyl ether, diethylene glycol mono-3-methyl butyl ether, diethylene glycol mono-2-pentyl ether, diethylene glycol mono-2
  • n-butyltriglycol ether may be used in combination with n-butyldiglycol ether, n-butyl tetraglycol ether and n-butyl pentaglycol ether.
  • the solvent comprises 75 w/w % n-butyltriglycol ether, 2.5 w/w % n-butyldiglycol ether, 19.0 w/w % n-butyl tetraglycol ether and 2.0 w/w % n-butyl pentaglycol ether.
  • the non-ionic amphiphilic solvent has a large capacity to solubilise or dissolve metal ions.
  • the metal ions in the crude oil partition into the non-ionic amphiphilic solvent (which is immiscible with the crude oil).
  • the resulting non-ionic amphiphilic solvent phase is thus a metal ion-containing phase, which is subsequently separated from the crude oil.
  • This separation step may be carried out using a density separator, for example, a decanter or hydrocyclone.
  • the non-ionic amphiphilic solvent is believed to couple the oil and water together forming a middle phase having a density intermediate between that of oil and water. This is believed to be possible because of the miscibility gap between the water and crude oil.
  • the middle phase exhibits low interfacial tension between the oil and water, and has a large capacity to solubilise or dissolve metal ions.
  • the middle phase is thus a metal ion-containing phase.
  • the crude oil may subsequently be separated from the middle phase (metal ion-containing phase) and water using a density separator, for example, a decanter or hydrocyclone.
  • the middle phase may not appear in the presence of water, until the reaction mixture is heated above a threshold temperature.
  • the middle phase does not become apparent until the crude oil/water/solvent mixture is heated to approximately 70° C. Below this temperature, the non-ionic amphiphilic solvent is substantially miscible with water.
  • This non-ionic amphiphilic solvent/water mixture may nevertheless have the capacity to dissolve metal ions.
  • the metal ions in the crude oil may become suspended in the non-ionic amphiphilic solvent/water phase.
  • This solvent/water phase is a metal-containing phase, which may be separated from the crude oil directly.
  • the crude oil/water/solvent system may be heated to at least 70° C., so as to produce the middle phase.
  • This middle phase is the metal-ion containing phase, which is subsequently separated.
  • the threshold temperature may vary depending on the nature of the non-ionic amphiphilic solvent employed. It may be possible to lower this threshold temperature by using mixtures of two or more solvents.
  • metal-containing phase it may be desirable to treat the metal-containing phase, so as to separate the metal ions from the non-ionic amphiphilic solvent. This allows the non-ionic amphiphilic solvent to be recycled for reuse.
  • Metal ions may be separated from the non-ionic amphiphilic solvent by distilling off the solvent. Alternatively, the metal ions may be removed from the non-ionic amphiphilic solvent using a membrane or an ion-exchange column. It may also be possible to separate the metal ions by using another solvent extraction step.
  • the crude oil may be contacted with the non-ionic amphiphilic solvent at a temperature of up to 160° C.
  • the crude oil is contacted with the non-ionic amphiphilic solvent at a temperature above the threshold temperature.
  • the contact temperature may range between ambient temperature and 160° C., preferably, between 70 and 160° C., more preferably, between 80 and 125° C., and most preferably, between 80 and 100° C. If a temperature of above 100° C. is employed, it may be desirable to operate the process at elevated pressure, for example at 5 to 20 bar.
  • the non-ionic amphiphilic solvent is preferably contacted with the crude oil in the presence of water.
  • the crude oil may contain some formation, connate, injection, aquifer and/or nascent water.
  • at least some of the water present during the contacting step is added to the crude oil. Addition of fresh water is advantageous since this will lower the salinity of the aqueous phase, thereby lowering the threshold temperature.
  • the concentration of non-ionic amphiphilic solvent in water may be between, 8 and 70 w/w %, preferably, between 15 and 60 w/w %.
  • the amount of non-ionic amphiphilic solvent employed may form 5 to 40, preferably, 10 to 30 wt % of the total amount of oil, amphiphilic solvent and optional water in the reaction mixture. Where water is present, it may 5 to 40, preferably, 10 to 30 wt % of the reaction mixture.
  • the resulting mixture may be stirred or agitated in a mixing unit.
  • the mixture may be stirred using a mechanical stirrer, an ultrasonic stirrer or by bubbling an inert gas through the reaction mixture.
  • the mixing step may last 2 to 30 minutes, preferably, 5 to 20 minutes and most preferably, 8 to 15 minutes.
  • the mixing step may be carried out at a temperature of 5 to 160° C., preferably 10 to 70° C., most preferably, 20 to 50° C., and especially 30 to 40° C.
  • the reaction mixture is then preferably heated to above the threshold temperature.
  • the crude oil may be desirable to contact the crude oil with the non-ionic amphiphilic solvent in the presence of an organic diluent, such as decane, gasoline, gas oil, diesel or kerosene.
  • an organic diluent such as decane, gasoline, gas oil, diesel or kerosene.
  • the process of the present invention may be used to remove any metal ions, including those in Groups IA and IIA of the Periodic Table from crude oil.
  • metal ions include sodium, potassium, magnesium, and in particular, calcium.
  • These metal ions may be present in any form, for example, as naphthenate, chloride, phenolate and/or sulphate salts. These salts may be formed when neutralising agents such as metal hydroxides, oxides and/or carbonates are contacted with the crude oil. Accordingly, the process of the present invention provides a convenient method of removing the salts produced when deacidifying crude oil from crude oil.
  • a further aspect of the present invention provides a process for reducing the acidity of crude oil comprising
  • the non-ionic amphiphilic solvent employed may be contacted with the crude oil before, after or at the same time as the metal-containing neutralising agent.
  • the non-ionic amphiphilic solvent is contacted with the oil after the metal-containing neutralising agent.
  • Suitable nonionic amphiphilic solvents have been described in relation to the first aspect of the present invention. As described above, the non-ionic amphiphilic solvent draws metal ions from the crude oil into a metal ion-containing phase: this metal-ion containing phase may subsequently be separated from the crude oil.
  • the metal containing neutralising agent is suitably a metal hydroxide, oxide or carbonate.
  • Group IA and IIA hydroxides and oxides for example, those of sodium, potassium, barium, calcium and magnesium are preferred. Of these, hydroxides of sodium potassium and in particular, calcium are most preferred.
  • These hydroxides neutralise acids, such as naphthenic acids, which are present in crude oil, producing water and neutralisation salts eg metal naphthenates.
  • the concentration of water present in the neutralisation step may be 0.01 to 100 wt % of oil.
  • Water is believed to aid the neutralisation reaction by catalysing the transfer of hydrogen ions between the oil and neutralising agent. For these reasons, water may have to be added to the reaction mixture. Some crude oils, however, may themselves contain sufficient water to aid the transfer of hydrogen ions. In such cases, the addition of water may not be necessary.
  • water concentrations of 0.01 to 30, more preferably 0.01 to 25 wt %, even more preferably, 0.1 to 20 wt %, most preferably, 3 to 20 wt %, and especially 10 to 15 wt % are employed during the deacidification step.
  • the non-ionic amphiphilic solvent is contacted with the crude oil after neutralisation, it may be desirable to remove some or substantially all of the water dispersed in the crude oil phase before the solvent is added, to ensure that the amphiphilic solvent is not diluted or is not diluted to too high a degree.
  • One way of removing the water is to use a demulsifier.
  • the demulsifier may cause the crude oil/neutralising agent mixture to separate into three phases: an oil-rich phase, an aqueous phase and an interface or “ragging” layer, disposed between the oil-rich and aqueous phases.
  • the non-ionic amphiphilic solvent may be added directly to this three-phase mixture.
  • the oil-rich phase may first be recovered from the three-phase mixture.
  • the non-ionic amphiphilic solvent may then be added to the recovered oil-rich phase, preferably in the presence of water.
  • demulsifier suitable for breaking water-in-oil type emulsions may be employed.
  • the demulsifier comprises at least one surfactant selected from the group consisting of:
  • polyamine salts such as polyester amines, amino methylated poly acrylamide, poly di-methyl amino propyl methacrylamide, poly dimethyl amino ethyl acrylate, poly ethylene imine, poly vinyl pyrrolidone, caprolactam-based polymers and quaternised versions of the above.
  • the molecular weight of the polyamine salt is above 3000;
  • polyethers such as copolymers of ethylene oxide and propylene oxide and the reaction products of such copolymers with diacids, diepoxides, diisocyanates, aldehydes, and diamines.
  • the molecular weight of the polyether is above 2000.
  • the demulsifier comprises a solution of the surfactant(s) dissolved in a solvent such as monoethylene glycol (MEG), tetraethylene glycol (TEG), butylethylene glycol (BGE), butyldiethylene glycol (BDGE), water, xylene and toluene.
  • a solvent such as monoethylene glycol (MEG), tetraethylene glycol (TEG), butylethylene glycol (BGE), butyldiethylene glycol (BDGE), water, xylene and toluene.
  • Suitable demulsifiers may also be prepared by reacting I) an addition product of a phenol and formaldehyde or acetaldehyde, with II) a block polymer containing nitrogen.
  • I) an addition product of a phenol and formaldehyde or acetaldehyde with II) a block polymer containing nitrogen.
  • the mole ratio of I to II is 1-20:1.
  • the addition product (I) may be obtained by reacting phenol with formaldehyde or acetaldehyde in a molar ratio of 1:1 to 3, preferably 1:1.8 to 2.2 at a temperature of 50° to 80° C., in the presence of an alkaline catalyst.
  • the block polymer (II) may be obtained by an addition reaction between ethylene oxide, propylene oxide and ethylenediamine, propylenediamine, polyethylenepolyamines, polypropylenepolyamines or mixtures thereof.
  • 10 to 80 moles, more preferably, 30 to 70 moles, of ethylene oxide and propylene oxide are added, as a statistical average per nitrogen atom.
  • the molar ratio of ethylene oxide to propylene oxide is 1:0.5 to 14, preferably, 1:1 to 8. Suitable demulsifiers are described in U.S. Pat. No. 4,474,682.
  • a preferred demulsifier is ML 3407TM (supplied by Baker Petrolite).
  • the concentration of demulsifier employed may be 0.01 to 5 wt %, preferably, 0.1 to 2 wt % and especially 0.1 to 0.5 wt % of oil.
  • the process of the present invention may be carried out on a refinery, or whilst the oil is being transported, for example, in a tanker at sea.
  • the oil-rich phase was recovered from this 3 phase mixture and found to have a Ca ion concentration of approximately 9 ppm. This showed that Ca ions originally present in the crude oil were removed by the addition of the non-ionic amphiphilic solvent.

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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)
US10/296,598 2000-05-30 2001-05-17 Process for removing metal ions from crude oil Abandoned US20030150779A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0013086.4 2000-05-30
GBGB0013086.4A GB0013086D0 (en) 2000-05-30 2000-05-30 Process for removing metal ions from crude oil

Publications (1)

Publication Number Publication Date
US20030150779A1 true US20030150779A1 (en) 2003-08-14

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US10/296,598 Abandoned US20030150779A1 (en) 2000-05-30 2001-05-17 Process for removing metal ions from crude oil

Country Status (6)

Country Link
US (1) US20030150779A1 (fr)
EP (1) EP1294827A1 (fr)
CN (1) CN1662631A (fr)
AU (1) AU5855701A (fr)
GB (1) GB0013086D0 (fr)
WO (1) WO2001092439A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007086661A1 (fr) * 2006-01-25 2007-08-02 Sk Energy Co., Ltd. Procédé permettant d'éliminer le calcium d'une huile hydrocarbonée
US8211294B1 (en) * 2011-10-01 2012-07-03 Jacam Chemicals, Llc Method of removing arsenic from hydrocarbons
US8241491B1 (en) * 2011-10-01 2012-08-14 Jacam Chemicals, Llc Method of removing arsenic from hydrocarbons
US8961794B2 (en) 2010-07-29 2015-02-24 Phillips 66 Company Metal impurity and high molecular weight components removal of biomass derived biocrude

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002953252A0 (en) * 2002-12-09 2003-01-02 Huntsman Corporation Australia Pty Ltd Compositions, Compounds and Methods for their Preparation
CN1208434C (zh) * 2003-06-03 2005-06-29 克拉玛依市金山石油化工有限公司 烃油脱金属剂及其制备方法和使用方法
CN103937530B (zh) * 2013-01-21 2016-08-03 中国石油化工股份有限公司 一种重油的处理方法
CN110240928B (zh) * 2019-06-21 2021-05-04 四川轻化工大学 一种柴油的脱酸精制方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU730026B2 (en) * 1996-10-04 2001-02-22 Exxon Research And Engineering Company Removal of calcium from crudes
GB9912842D0 (en) * 1999-06-02 1999-08-04 Bp Exploration Operating Process for reducing the acidity of oil

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007086661A1 (fr) * 2006-01-25 2007-08-02 Sk Energy Co., Ltd. Procédé permettant d'éliminer le calcium d'une huile hydrocarbonée
US8961794B2 (en) 2010-07-29 2015-02-24 Phillips 66 Company Metal impurity and high molecular weight components removal of biomass derived biocrude
US8211294B1 (en) * 2011-10-01 2012-07-03 Jacam Chemicals, Llc Method of removing arsenic from hydrocarbons
US8241491B1 (en) * 2011-10-01 2012-08-14 Jacam Chemicals, Llc Method of removing arsenic from hydrocarbons

Also Published As

Publication number Publication date
AU5855701A (en) 2001-12-11
EP1294827A1 (fr) 2003-03-26
CN1662631A (zh) 2005-08-31
WO2001092439A1 (fr) 2001-12-06
GB0013086D0 (en) 2000-07-19

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Owner name: BP EXPLORATION OPERATING COMPANY LIMITED, ENGLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:COLLINS, IAN RALPH;DUNCUM, SIMON NEIL;OSBOURNE, CHRISTOPHER GEORGE;REEL/FRAME:014014/0801;SIGNING DATES FROM 20021014 TO 20021114

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION