US3725250A - Process for improving a hydrocarbon charge stock by contacting the charge with water at elevated temperature and pressure - Google Patents

Process for improving a hydrocarbon charge stock by contacting the charge with water at elevated temperature and pressure Download PDF

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Publication number
US3725250A
US3725250A US00108859A US3725250DA US3725250A US 3725250 A US3725250 A US 3725250A US 00108859 A US00108859 A US 00108859A US 3725250D A US3725250D A US 3725250DA US 3725250 A US3725250 A US 3725250A
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United States
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oil
percent
water
charge
gas
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US00108859A
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English (en)
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R Wilson
R Peck
H Hess
N Carter
E Cole
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Texaco Inc
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Texaco Inc
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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
    • C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
    • 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
    • C10G21/08—Inorganic compounds only

Definitions

  • Oil refining is effected by heating under agitated flow conditions crude oil or residual oil with water at a temperature sufficient to form a foam which is cooled below the vaporization temperature of water to form a stable emulsion containing sulfur, carbon residues, asphaltenes, nickel and vanadium. After removal of the emulsion, the oil can be used as a fuel or in catalytic processes.
  • This invention relates to a process for upgrading crude or residual oils by the removal of certain contaminants as well as to the use of such upgraded oils in a cracking process for the production of high quality hydrocarbons.
  • Heavy hydrocarbon fractions contain a considerable quantity of contaminating components such as asphaltenes, trace metals, carbon residues as well as sulfurous compounds.
  • contaminating components such as asphaltenes, trace metals, carbon residues as well as sulfurous compounds.
  • the presence of such contaminants renders these oils unsatisfactory for inclusion in boiler fuels, turbine fuels and the like because of the odor emissions, gum and varnish formation they occasion.
  • the presence of sulfur, of asphaltenic materials which are coke precursors, and of organometallic compounds rapidly deactivates most catalysts. It is, therefore, very desirable to remove these contaminants from an oil before refining.
  • the main object of the present invention is to provide means for converting large quantities of poor quality stock without the use of expensive solvents or of hydrogen.
  • An equally important object of the invention is the utilization in a catalytic cracking process of an oil converted as indicated in the above manner so as to produce higher liquid yields at lower coke yields.
  • the oil and water mixture are raised to a temperature in the heated reaction coil sufiicient to form a foam or disperse system which consists of water vapor (steam) being the disperse phase and the oil being the dispersion medium.
  • Flow through the coil provides agitation to the mixture.
  • the temperature in the reaction coil must be sufficient such that when the foam or disperse system is cooled below the vaporization temperature of water a stable emulsion is formed with the contaminants hereinbefore mentioned.
  • the efiluent from the reaction coil flows to a gas-liquid separator 4 where it is cooled to condense the water vapor and to form the stable emulsion.
  • the light hydrocarbon gases formed in the reaction coil are removed from the gas-liquid separator through line 5.
  • the liquid phase remaining comprises a stable emulsion dispersed in the treated oil.
  • the liquids then pass through line 6 into filter 7 where the stable emulsion containing the contaminants is withdrawn through line 8.
  • the emulsion may be further processed in known manner so as to recover valuable metals such as nickel and vanadium which may be present therein.
  • the material goes to stripper 10 where water is removed through line 11.
  • the decontaminated oil which now has a higher API gravity is withdrawn through line 12. It is important to note that at this point the oil is pure enough to be used as fuel or the like; but it may be further processed.
  • the oil is sent onto a fluid catalytic cracking unit 13 containing cracking catalysts and the products are withdrawn through line 14.
  • Example I In the series of tests constituting this example an oil containing a large amount of sulfur, carbon residue, and asphaltenes and a small amount of trace metals is mixed with water vapor (steam) to form a dispersed system and treated under the conditions shown.
  • the reaction vessel used in these tests is a 1 /2 inch I.D. reactor packed with Berl saddles.
  • the dispersed system consisting of water vapor in oil is withdrawn from the reaction vessel at the treating temperature, cooled to about 150 F. to form a stable emulsion containing the contaminants dispersed in the treated oil, and the stable emulsion is separated from the treated oil at about 150 F. by filtration.
  • Table I lists tests performed on the contaminant-com taining oils used in this and the following example.
  • Table II lists operating data and product quality tests noted when applying this process for the removal of contaminants from Arabian Atmospheric Reduced Crude. It will be noted from the data in Table II that the present process can be employed at 800 F. to remove a large portion of the contaminants present in the oil and to convert an appreciable portion of the 850 F. material. However, it will also be noted that when processing the oil at lower temperatures (600 and 700 F.) a stable emulsion does not form.
  • Example II In the series of tests constituting this example, an oil containing a large amount of nickel and vanadium as Well as moderate amounts of sulfur, carbon residue, and asphaltenes was treated in the presence of water under the conditions of Example I.
  • Table III lists operating data and product quality tests when applying this process for the removal of contaminants from Lago Medio Atmospheric Reduced Crude. It will be noted that the process of this disclosure may be employed to remove a large portion of the trace metals present in the oil. It will also be noted that the amount of the stable emulsion which forms increases with temperatures and that the removal of contaminants from the charge oil does not occur at 600 and 700 F. even though an emulsion formed. Only at 800 F. was there a reduction in the metals and carbon residue content as shown by the product oil tests.
  • Example III In another test, Lago Medio Atmospheric Reduced Crude was treated in a manner used in Examples I and II except that no water was admixed with nor included in the feedstock. Data for this test are given in Table IV.
  • Example IV In this example an oil containing a large amount of sulfur, carbon residue, asphaltenes and trace metals was treated in the presence of water under the conditions of Ex. I.
  • the reaction vessel used in this test was a 1 /2 inch I.D. reactor packed with Berl saddles. The treated oil and stable emulsion were withdrawn as a suspension and separated by filtration.
  • the treated oil was then charged in three separate and equal portions of 0.8 gram each over 2.5 grams of Davison XZ 25 plus cracking catalyst.
  • the catalyst was calcined for 6 hrs. in a muflle furnace at 1000" F. prior to being placed in the Vycor reactor. A /z inch layer of mullite chips were placed in the reactor to act as a preheater.
  • the catalyst was then calcined for 1% hours at 1000 F. using 25 ml./min. of helium to purge. The temperature was then reduced to 900 F. and the helium flow adjusted to 15 ml./min.
  • Each hydrocarbon sample was injected into the reactor /2 inch above the mullite chips within l00160 sec. The helium flush was then continued for 30 minutes.
  • the liquid product was collected from each separate run in a 10 cc. vial at 32 F. and the gas was collected in plastic bags.
  • the liquid samples were weighed and analyzedby gas chromatography for peaks up to C
  • the gas samples, (3,; to C were also analyzed by gas chromatography and the weight of hydrocarbon in the gas was calculated from peak height and gas volume.
  • Example V In this example a sample of raw Arabian Atmospheric Reduced Crude was catalytically cracked without pretreatment. The cracking was carried out in the same way as described in Example IV.
  • Example VI In this example Arabian Heavy Vacuum Gas Oil and a furfural extract from Arabian Heavy Cycle Gas were treated in the presence of water to remove carbon residue and trace metals. Both of these stocks were treated at the same conditions as the Arabian Atmospheric Reduced Crude was in Example IV. The results of these evaluations are shown in Table VII and indicated that these stocks when treated with water at high temperatures followed by removal of the stable emulsion would be more suitable for catalytic cracking than the raw stocks were.
  • a process for improving the quality of crude oil or residual oil containing sulfur, carbon residues, asphaltenic material and trace metal contaminants comprising: heating said charge stock under agitated flow conditions with from about 5% to about 100% by weight of water based on the weight of said stock at a temperature ranging from about 500 to about 1000 F. at a pressure ranging from about 0 to about 600 p.s.i.g. to form a disperse system consisting of water vapor as the disperse phase and said stock as the dispersion medium; cooling said system to about 100 to 210 F. at a pressure of about 0 to 600 p.s.i.g. to form a stable emulsion with said contaminants; removing light hydrocarbon gases formed at said temperature and separating said contaminants-containing emulsion from said stock, said stock now having a higher API gravity and being substantially free of said contaminants.
  • hydrocarbon charge stock is selected from the group of residual oils, whole crudes, gas oils, cycle oils and coker oils.
  • said cracking catalyst is silica-alumina or a synthetic silicaalumina zeolite.

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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)
  • Inorganic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US00108859A 1971-01-22 1971-01-22 Process for improving a hydrocarbon charge stock by contacting the charge with water at elevated temperature and pressure Expired - Lifetime US3725250A (en)

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US (1) US3725250A (enrdf_load_stackoverflow)
JP (1) JPS5021483B1 (enrdf_load_stackoverflow)
DE (1) DE2202526A1 (enrdf_load_stackoverflow)
GB (1) GB1341362A (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4347122A (en) * 1979-11-14 1982-08-31 Ashland Oil, Inc. Carbo-metallic oil conversion with liquid water
US4366045A (en) * 1980-01-22 1982-12-28 Rollan Swanson Process for conversion of coal to gaseous hydrocarbons
US4366044A (en) * 1979-08-06 1982-12-28 Rollan Swanson Process for conversion of coal to hydrocarbon and other values
US4405445A (en) * 1981-08-24 1983-09-20 Ashland Oil, Inc. Homogenization of water and reduced crude for catalytic cracking
US4428828A (en) 1981-01-02 1984-01-31 Chevron Research Company Upgrading hydrocarbonaceous oils with an aqueous liquid
US4468316A (en) * 1983-03-03 1984-08-28 Chemroll Enterprises, Inc. Hydrogenation of asphaltenes and the like
US4606812A (en) * 1980-04-15 1986-08-19 Chemroll Enterprises, Inc. Hydrotreating of carbonaceous materials
EP1767609A1 (en) * 2005-09-26 2007-03-28 Hitachi, Ltd. Method for producing gas turbine fuel, and method and system for generating electric power by gas turbine

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5280135U (enrdf_load_stackoverflow) * 1975-12-12 1977-06-15
DE60030168D1 (de) * 2000-05-15 2006-09-28 Texaco Development Corp Dampfphaseneutralisierung in integriertem lösungsmittelentasphaltierungs- und vergasungsverfahren
DE102013106439A1 (de) * 2013-06-20 2014-12-24 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Verfahren zur Entfernung von Metallen aus hochsiedenden Kohlenwasserstofffraktionen

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4366044A (en) * 1979-08-06 1982-12-28 Rollan Swanson Process for conversion of coal to hydrocarbon and other values
US4347122A (en) * 1979-11-14 1982-08-31 Ashland Oil, Inc. Carbo-metallic oil conversion with liquid water
US4366045A (en) * 1980-01-22 1982-12-28 Rollan Swanson Process for conversion of coal to gaseous hydrocarbons
US4606812A (en) * 1980-04-15 1986-08-19 Chemroll Enterprises, Inc. Hydrotreating of carbonaceous materials
US4428828A (en) 1981-01-02 1984-01-31 Chevron Research Company Upgrading hydrocarbonaceous oils with an aqueous liquid
US4405445A (en) * 1981-08-24 1983-09-20 Ashland Oil, Inc. Homogenization of water and reduced crude for catalytic cracking
US4468316A (en) * 1983-03-03 1984-08-28 Chemroll Enterprises, Inc. Hydrogenation of asphaltenes and the like
EP1767609A1 (en) * 2005-09-26 2007-03-28 Hitachi, Ltd. Method for producing gas turbine fuel, and method and system for generating electric power by gas turbine
US20070215522A1 (en) * 2005-09-26 2007-09-20 Shinichi Inage Method for producing gas turbine fuel, and method and system for generating electric power by gas turbine
US7611676B2 (en) 2005-09-26 2009-11-03 Hitachi, Ltd. Method for producing gas turbine fuel, and method and system for generating electric power by gas turbine

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Publication number Publication date
GB1341362A (en) 1973-12-19
JPS5021483B1 (enrdf_load_stackoverflow) 1975-07-23
DE2202526A1 (de) 1972-07-27

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