US2897144A - Removal of metallic contaminants from hydrocarbon oils with a foaming agent - Google Patents

Removal of metallic contaminants from hydrocarbon oils with a foaming agent Download PDF

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Publication number
US2897144A
US2897144A US70204057A US2897144A US 2897144 A US2897144 A US 2897144A US 70204057 A US70204057 A US 70204057A US 2897144 A US2897144 A US 2897144A
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US
United States
Prior art keywords
oil
line
foam
gas
foaming
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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
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English (en)
Inventor
Herman Bieber
Ibrahim A Eldib
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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
Priority to NL112071D priority Critical patent/NL112071C/xx
Application filed by Exxon Research and Engineering Co filed Critical Exxon Research and Engineering Co
Priority to US70204057 priority patent/US2897144A/en
Priority to GB31955/58A priority patent/GB830128A/en
Priority to DEE16626A priority patent/DE1129251B/de
Priority to FR781343A priority patent/FR1217278A/fr
Application granted granted Critical
Publication of US2897144A publication Critical patent/US2897144A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/02—Froth-flotation processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/08—Subsequent treatment of concentrated product
    • B03D1/082—Subsequent treatment of concentrated product of the froth product, e.g. washing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/14—Flotation machines
    • B03D1/1443—Feed or discharge mechanisms for flotation tanks
    • B03D1/145—Feed mechanisms for reagents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/14—Flotation machines
    • B03D1/1443—Feed or discharge mechanisms for flotation tanks
    • B03D1/1456—Feed mechanisms for the slurry
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/14—Flotation machines
    • B03D1/1443—Feed or discharge mechanisms for flotation tanks
    • B03D1/1462—Discharge mechanisms for the froth

Definitions

  • the present invention relates to the upgrading of hydrocarbon oils and more particularly relates to a new and improved refining process for removing innate organo-metallic compounds and other surface active materials from hydrocarbon oils.
  • Organo-metallic compounds are found as innate constituents in most petroleum gas oils and residua boiling in excess of about 950 F. and may be present therein in concentrations as high as 200 pounds per 1000 barrels of oil. Because of the presence of these metallic compounds, such oils are unsuitable for use as high grade fuels, as feed stocks to catalytic cracking units and in other applications of similar nature. In catalytic cracking and hydrofining processes, for example, Imetallic compounds in the feed streams will quickly deactivate the catalysts and cause the production of large amounts of coke and gases.
  • the present invention provides a new and improved method for removing innate organo-metallic compounds and other surface active constituents from hydrocarbon oils and thus opens the way lfor the use of such oils in a variety of applications for which they have been unsuitable heretofore.
  • organo-metallic constituents of hydrocarbon oils can be readily removed from such oils by introducing gas into the oils under conditions such that a stable foam is produced. It has been found that these constituents are collected by the gas bubbles as they pass upwardly through the oil and are concentrated at the gas-liquid interfaces in the foam above the oil phase. By separating the foam containing the metals from the oil, oil of substantially reduced metals content can be obtained.
  • the invention provides a process for the removal of innate metallic compounds from hydrocarbon oils which is both highly effective and economically attractive.
  • the process of the invention which may be referred to as foam fractionation, can be better understood by rst considering the nature and properties of the metallic compounds found in hydrocarbon oils. These compounds are innate constituents of crude oil which upon distillation appear in the heavy fractions boiling above about 950 F. They are nonvolatile at temperatures below about l050 F. and are thus present in distillates having an upper end point between 950 and 1050u F. as a result of entrainment during fractionation. Analyses have shown that the metals are usually complex organic compounds of the porphyrin type in which a central atom of iron, nickel, vanadium or a similar metal is surrounded by four pyrole rings interconnected by 2,897,144 Patented July 28, 1959 methene linkages. Various substituents including alkyl chains, alkylene groups and carboxylic acid radicals may be attached to each of the pyrrole rings and in some cases the individual porphyrin molecules may polymerize to give even more complex structures.
  • the metallic constituents found in high boiling hydrocarbon oils exhibit a high degree of surface activity. This provides a means for their separation from the bulk of the oil which is nonsurface active. By providing a large phase interface at which surface-active materials tend to concentrate to the exclusion of non-surface active constituents, a separation can be made between the metallic compounds and the bulk of the oil. Foaming the oil provides the necessary phase interface.
  • gas is introduced into oil, foam is formed and the surfaceactive constituents are concentrated in the oil-gas interfaces surrounding the gas bubbles and are thus carried into the foam phase above the oil.
  • the foam is withdrawn overhead from the foaming vessel and oil of reduced metals content is taken off as a bottoms product.
  • the foam recovered may be collapsed and a part of the oil obtained therefrom may be reuxed to enrich Subsequent foam in metals content and reduce the loss of oil.
  • the gas employed for the production of foam in accordance with the invention is not critical and any of a number of gases commonly available may be rutilized. These include inert gases such as carbon dioxide and nitrogen; hydrocarbons such as methane, ethane, ethylene, propane, propylene, butane and mixtures of refinery gases; and other gases such as air, ammonia, oxygen and steam. Gases which can be readily condensed, particularly the heavier hydrocarbon gases and superheated steam, are often preferred because they permit collapse of the foam by condensation and facilitate the recovery of any volatile components of the oil which may have been distilled oif during the foaming process.
  • gases which can be readily condensed, particularly the heavier hydrocarbon gases and superheated steam, are often preferred because they permit collapse of the foam by condensation and facilitate the recovery of any volatile components of the oil which may have been distilled oif during the foaming process.
  • hydrocarbon oils which may be treated for the removal of metallic contaminants in accordance with the invention in general are those including constituents boiling in excess of about 950 F.
  • metallic compounds are found only in oils boiling above about 950 F.
  • the presence of lower boiling constituents in the oils treated by the process is not objectionable andin most cases is desirable because of the high viscosities of fractions boiling wholly above 950 F. It has been found that viscosity has a pronounced effect upon the foaming properties of oils and that some very heavyV fractions will not foam satisfactorily. It is therefore preferred to treat broad fractions having initial boiling points well below 950 F. or to dilute the heavy fractions boiling above that temperature with low viscosity hydrocarbon diluents prior to treating.
  • Preferred diluents include aliphatic hydrocarbon solvents boiling between about 200 F. and about 400 F., kerosines, heavy naphthas and the like. Water may also be added to the oils to promote foaming but this is not always satisfactory because of the emulsion problems sometimes encountered.
  • the gas may be introduced into the oil in a number of diiferent ways.
  • the simplest and preferred method consists of injecting the gas through one or more orifices located beneath the oil surface.
  • a sparge, a perforated plate or the like may be used in order to distribute the gas bubbles and obtain better contact with the oil than can be had when a single orifice is used.
  • Alternate procedures for introducing the gas include the injection of liquefied gases into the oil at controlled rates so that they vaporize l therein and the use of various agitating devices.
  • the foam produced in carrying out the process of the invention can usually be collapsed by simply passing it from the foaming vessel into a separation vessel.
  • Foam persistence is governed by the surface tension and viscosity ofthe oil, the bubble size and the temperature and a foam which will readily collapse upon reaching the separation vessel can generally'be produced by regulating the solvent-to-oil ratio, the size of the orifices through which the gas is introduced and the operating temperature.
  • Other well known methods of collapsing foams such as sudden changes in temperature or pressure or electrical fields, may also be used.
  • lf a condensible vapor such as steam is used as the foaming gas
  • the foam may be collapsed by condensation as mentioned heretofore. This method will, or course, require separation of the condensed vapor from the oil by decanting, ashing or the like before the oil is refluxed to the foaming step of the process.
  • a hydrocarbon oil containing constituents boiling above about 950 F. and including metallic constituents of the porphyrin type is introduced into foaming vessel 1 through line 2.
  • the foaming vessel should be a vertical tower having suicient space therein to permit enrichment of the foam in contaminants content by refluxing action.
  • Feed line 2 terminates within the foaming vessel in a spray head 3 by means of which the feed may be evenly distributed over the cross-section of the vessel.
  • Kerosine or other suitable hydrocarbon solvent is introduced into the foaming vessel through line 4 and spray nozzle 5. Alternatively the solvent may instead be mixed with the oil and introduced concomitant therewith.
  • Preferred solvent-to-oil ratios range between about 1:1 and about 4:1.
  • the solvent selected should be substantially nonvolatile at the temperature employed in carrying out the process in order to avoid undue solvent losses by evaporation.
  • Air or other gas is introduced at ambient temperature into the bottom of foaming vessel 1 through line 6 and sparge or other distribution device 7 and bubbled upwardly through the oil therein.
  • the oil level in the vessel is indicated by reference numeral S and is maintained at an intermediate point between the levels at which the feed and gas are introduced.
  • Vessel 1 may be provided with coils, jacketing or other heating means in order to maintain the proper temperature therein. Unduly high temperatures should be avoided, since they may interfere with the foaming action.
  • the linear velocity of the gas introduced into the foaming vessel may be varied widely depending upon the diameter of the vessel and the viscosity of the liquid. It has, however, been found that the height of the foam phase increases with gas velocity and then drops again. A high foam phase permits oil in the foam to drain back into the oil pool at the bottom of the foaming vessel and thus results in improved separation. Conditions for maximum foam height can be readily determined experimentally for any system.
  • the foam is collapsed in the defoaming zone and air is vented therefrom through line 12.
  • Oil and metallic compounds carried overhead from vessel 1 in the foam are removed from the defoaming zone through line 13.
  • a portion of this metals-containing oil is withdrawn from the system through line 14 but the major part is transferred through line 15 and spray nozzle 16 into the upper part of vessel 1 as reflux.
  • Reflux ratios may range from 1:1 to as much as 10:1 or higher.
  • the reiiux oil rich in metals passes downwardly through the vessel countercurrent toV the rising foam.
  • Metals present in the reflux are stripped therefrom by the foam and thus the concentration of metals in the foam is increased.
  • the reux oil from which the metals are stripped serves to increase the product oil yield.
  • a distillation step, not shown, may be employed for removing the solvent from the product oil.
  • the invention may be illustrated still further by considering experiments which were carried out for the removal of metallic porphyrins from a hydrocarbon oil by foam fractionation.
  • An improved process for removing surface active constituents from a hydrocarbon oil which comprises foaming a portion of said oil with a non-reactive gas and separately recovering foam containing surface active compounds and oil substantially reduced in surface active constituents.
  • An improved process for removing surface active constituents from a hydrocarbon oil which comprises foaming a portion of said oil with a non-reactive gas, separately recovering foam containing surface active compounds and oil substantially reduced in surface active constituents, collapsing said recovered foam and recovering oil containing surface active compounds therefrom, and reuxing a portion of said oil containing surface active compounds in countercurrent contact with foam from said foaming step.
  • An improved process for removing metallic porphyrins from a petroleum fraction including constituents boiling in excess of about 950 F. which comprises bubbling a non-reactive gas through said oil and forming a foam in which porphyrins are concentrated, separately withdrawing foam containing porphyrins and oil having a substantially reduced porphyrins content, collapsing said withdrawn foam and recovering oil containing porphyrins, and refluxing a portion of said oil containing porphyrins in countercurrent contact with said foam containing porphyrins,

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biotechnology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Gas Separation By Absorption (AREA)
US70204057 1957-12-11 1957-12-11 Removal of metallic contaminants from hydrocarbon oils with a foaming agent Expired - Lifetime US2897144A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL112071D NL112071C (enrdf_load_stackoverflow) 1957-12-11
US70204057 US2897144A (en) 1957-12-11 1957-12-11 Removal of metallic contaminants from hydrocarbon oils with a foaming agent
GB31955/58A GB830128A (en) 1957-12-11 1958-10-07 Removal of surface-active contaminants from hydrocarbon oils
DEE16626A DE1129251B (de) 1957-12-11 1958-10-21 Verfahren zur Verminderung der Konzentration oberflaechenaktiver Stoffe in Kohlenwasserstoffoelen
FR781343A FR1217278A (enrdf_load_stackoverflow) 1957-12-11 1958-12-10

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US70204057 US2897144A (en) 1957-12-11 1957-12-11 Removal of metallic contaminants from hydrocarbon oils with a foaming agent

Publications (1)

Publication Number Publication Date
US2897144A true US2897144A (en) 1959-07-28

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ID=29401812

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US70204057 Expired - Lifetime US2897144A (en) 1957-12-11 1957-12-11 Removal of metallic contaminants from hydrocarbon oils with a foaming agent

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US (1) US2897144A (enrdf_load_stackoverflow)
DE (1) DE1129251B (enrdf_load_stackoverflow)
FR (1) FR1217278A (enrdf_load_stackoverflow)
GB (1) GB830128A (enrdf_load_stackoverflow)
NL (1) NL112071C (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998382A (en) * 1958-10-01 1961-08-29 Exxon Research Engineering Co Regeneration of spent caustic by foaming
US3339730A (en) * 1962-07-14 1967-09-05 Column Flotation Co Of Canada Froth flotation method with counter-current separation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2713420A (en) * 1954-05-18 1955-07-19 Southwestern Eng Co Clarification process
US2820759A (en) * 1954-05-04 1958-01-21 Gilbert P Monet Method of separating froths from liquids

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1739092A (en) * 1924-10-21 1929-12-10 Westinghouse Electric & Mfg Co Elimination of impurities in insulating oils
DE960846C (de) * 1952-07-14 1957-03-28 British Petroleum Co Verfahren zur Verminderung des Vanadium- und/oder Natriumgehaltes von rohem Erdoel oder Erdoelprodukten
US2902429A (en) * 1955-06-17 1959-09-01 California Research Corp Demetallization of hydrocarbon fractions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2820759A (en) * 1954-05-04 1958-01-21 Gilbert P Monet Method of separating froths from liquids
US2713420A (en) * 1954-05-18 1955-07-19 Southwestern Eng Co Clarification process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2998382A (en) * 1958-10-01 1961-08-29 Exxon Research Engineering Co Regeneration of spent caustic by foaming
US3339730A (en) * 1962-07-14 1967-09-05 Column Flotation Co Of Canada Froth flotation method with counter-current separation

Also Published As

Publication number Publication date
FR1217278A (enrdf_load_stackoverflow) 1959-12-07
GB830128A (en) 1960-03-09
DE1129251B (de) 1962-05-10
NL112071C (enrdf_load_stackoverflow)

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