US2687985A - Removal of vanadium and sodium from petroleum hydrocarbons - Google Patents

Removal of vanadium and sodium from petroleum hydrocarbons Download PDF

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Publication number
US2687985A
US2687985A US33266253A US2687985A US 2687985 A US2687985 A US 2687985A US 33266253 A US33266253 A US 33266253A US 2687985 A US2687985 A US 2687985A
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Prior art keywords
sodium
vanadium
removal
hydrocarbons
bauxite
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Porter Frederick Willi Bertram
Northcott Roy Purdy
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Anglo Iranian Oil Co Ltd
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Anglo Iranian Oil Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/22—Obtaining vanadium
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen

Definitions

  • This invention relates to the removal of vanadium and sodium from petroleum hydrocarbons in particular crude petroleum and petroleum residues.
  • vanadium removal is primarily a hydrogenation process which is dependent, among other things, upon the hydrogen partial pressure, while the removal of extraneous or uncombined sodium is primarily a physical process, the efliciency of which is not improved by the presence of hydrogen which competes with the sodium for the adsorbing surface of the bauxite. Whether this explanation is correct or not, it has been discovered that improved removal of vanadium and sodium may be effected by a twostage treatment over bauxite, only one stage being carried out in the presence of hydrogen.
  • a petroleum feedstock containing vanadium and uncombined sodium is passed first over bauxite at elevated temperature and pressure and in the absence of hydrogen, whereby substantially all the sodium is removed from the feedstock, and then over bauxite at elevated temperature and pressure and in the presence of hydrogen, whereby a considerable proportion of the vanadium is removed from the feedstock.
  • Both stages of the process are advantageously operated at a temperature of approximately 780 F. and a pressure of approximately 1000 lb./sq. in.
  • the invention may advantageously be carried into effect in a tower containing a single bed of bauxite, hydrogen being admitted to the tower at an intermediate point calculated to afford the optimum space Velocities for both sodium and vanadium removal.
  • the invention also includes a continuous process wherein a petroleum feedstock containing vanadium and sodium is passed first to a twostage bauxite treating process as above described and is then passed to a hydrofining zone wherein it is treated for the removal of organically combined sulphur.
  • the treated feedstock leaving the tower I2 is passed via line l3 to a hydrofining zone operated in known manner.
  • the tower I2 is divided into a lower part In and an upper part lZb, both parts being filled with bauxite, and recycle gas from the hydrofining zone is introduced into the tower between the two parts thereof via line 14 and heater l5.
  • a process for the removal of vanadium and sodium from petroleum hydrocarbons which comprises passing the hydrocarbons over bauxite at elevated temperature and pressure and in the absence of hydrogen, whereby substantially all the sodium is removed from the hydrocarbons, and then passing the hydrocarbons over bauxite at elevated temperature and pressure and in the presence of hydrogen, whereby a considerable proportion of the vanadium is removed from the hydrocarbons.
  • a process for the removal of vanadium and sodium from petroleum hydrocarbons which comprises passing the hydrocarbons through a bed of bauxite at elevated temperature and pressure, and admitting hydrogen to said bed at an intermediate point calculated to afiord optimum space velocities for both sodium and vanadium removal.
  • a process for the treatment of petroleum 0 hydrocarbons containing vanadium, sodium and organically combined sulphur which comprises passing the hydrocarbons over bauxite at elevated temperature and pressure and in the absence of 5 combined sulphur.

Description

W- B. PORTER ETAL REMOVAL OF VANADIUM AND SODIUM FROM PETROLEUM HYDROCARBONS Filed Jan. 22, 1953 OF HYDROFNING TO CATALYST REACTOR PLANT 2 uojAUXlTE ZONE FOR VANADIUM REMOVAL .RECYCLE GAS mm HYDROFlNlNG PLANT HEATER Rsc'vcn: GAS
IsT. sAuxn': 26M: FOR somum REMOVAL a INVENT OBS FREDERICK WILLIAM BERTRAM PORTER ROY PURDY NORTHCOTT 7M vylmA-h ATTORNEYS Patented Aug. 31, 1954 REMOVAL OF VANADIUM AND SODIUM FROM PETROLEUM HYDROCARBONS Frederick William Bertram Porter and Roy Purdy Northcott, Sunbury-onThames, England, assignors to Anglo-Iranian Oil Company Limited, London, England, a British joint-stockcorporation Application January 22, 1953, Serial Not 332,662
Claims priority, application Great Britain January 31, 1952 Claims.
This invention relates to the removal of vanadium and sodium from petroleum hydrocarbons in particular crude petroleum and petroleum residues.
In the specification of the co-pending application of Porter and Hyde No. 263,956, filed December 28, 1951, there is described a process for the removal of vanadium and sodium from petroleum hydrocarbons wherein the hydrocarbons are contacted with bauxite in the presence or absence of hydrogen and under conditions of temperature and pressure such that the sodium and vanadium are deposited on or incorporated with the bauxite. The removal of sodium and vanadium from a petroleum feedstock prior to hydrofining the feedstock is of particular advantage since it avoids contamination of the cobalt molybdate type catalyst commonly used in the hydrofining process, and such a two-stage process forms the subject of co-pending application of Porter and Hyde, No. 276,256 filed December 13, 1952. It has now been discovered that the conditions which are most favourable for the removal of vanadium from petroleum feedstocks are not the most favourable for the removal of sodium and vice versa. For example, on treating a Kuwait residue over bauxite at 780 F., 1000 p. s. i. ga., 1.0 v./v./hr. and 4000 SCF/B recycle rate, the vanadium removal over 100 hours was approximately 5 and the sodium removal 3 On treating the same feedstock over bauxite at 780" E, 1000 p. s. 1. ga. and 1.0 v./v./hr. but without hydrogen recycle, vanadium removal was only approximately whereas sodium removal was over 90%. The feedstock employed con;- tained 35 p. p. m. vanadium and 35 p. p. In. sodium, the bulk of the sodium being of extraneous origin introduced during distillation of the crude.
It is considered that vanadium removal is primarily a hydrogenation process which is dependent, among other things, upon the hydrogen partial pressure, while the removal of extraneous or uncombined sodium is primarily a physical process, the efliciency of which is not improved by the presence of hydrogen which competes with the sodium for the adsorbing surface of the bauxite. Whether this explanation is correct or not, it has been discovered that improved removal of vanadium and sodium may be effected by a twostage treatment over bauxite, only one stage being carried out in the presence of hydrogen.
According to the invention therefore, a petroleum feedstock containing vanadium and uncombined sodium is passed first over bauxite at elevated temperature and pressure and in the absence of hydrogen, whereby substantially all the sodium is removed from the feedstock, and then over bauxite at elevated temperature and pressure and in the presence of hydrogen, whereby a considerable proportion of the vanadium is removed from the feedstock.
Both stages of the process are advantageously operated at a temperature of approximately 780 F. and a pressure of approximately 1000 lb./sq. in.
The invention may advantageously be carried into effect in a tower containing a single bed of bauxite, hydrogen being admitted to the tower at an intermediate point calculated to afford the optimum space Velocities for both sodium and vanadium removal.
The invention also includes a continuous process wherein a petroleum feedstock containing vanadium and sodium is passed first to a twostage bauxite treating process as above described and is then passed to a hydrofining zone wherein it is treated for the removal of organically combined sulphur.
One embodiment of the process according to the invention is diagrammatically illustrated in the accompanying drawing.
A petroleum feedstock containing sodium and vanadium, such as crude oil or crude oil residue, is passed via line It and heater H into a tower l2. The treated feedstock leaving the tower I2 is passed via line l3 to a hydrofining zone operated in known manner. The tower I2 is divided into a lower part In and an upper part lZb, both parts being filled with bauxite, and recycle gas from the hydrofining zone is introduced into the tower between the two parts thereof via line 14 and heater l5.
We claim:
l. A process for the removal of vanadium and sodium from petroleum hydrocarbons, which comprises passing the hydrocarbons over bauxite at elevated temperature and pressure and in the absence of hydrogen, whereby substantially all the sodium is removed from the hydrocarbons, and then passing the hydrocarbons over bauxite at elevated temperature and pressure and in the presence of hydrogen, whereby a considerable proportion of the vanadium is removed from the hydrocarbons.
2. A process according to claim 1, wherein both stages of the process are operated at a temperature of approximately 780 F. and a pressure of approximately 1000 1b./sq. in.
3. A process for the removal of vanadium and sodium from petroleum hydrocarbons, which comprises passing the hydrocarbons through a bed of bauxite at elevated temperature and pressure, and admitting hydrogen to said bed at an intermediate point calculated to afiord optimum space velocities for both sodium and vanadium removal.
4. A process according to claim 3, wherein the bed of bauxite is maintained at a temperature of approximately 780 F. and a pressure of approximately 1000 1b./sq. in.
5. A process for the treatment of petroleum 0 hydrocarbons containing vanadium, sodium and organically combined sulphur, which comprises passing the hydrocarbons over bauxite at elevated temperature and pressure and in the absence of 5 combined sulphur.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,753,859 Gray Apr. 8, 1930 2,340,939 Davis et al Feb. 8, 1942 2,41 ,029 Oberfell Apr, 15, 1947 2,614,068 Healy et al Oct. 14, 1952

Claims (1)

1. A PROCESS FOR THE REMOVAL OF VANADIUM AND SODIUM FROM PETROLEUM HYDROCARBONS, WHICH COMPRISES PASSING THE HYDROCARBONS OVER BAUXITE AT ELEVATED TEMPERATURE AND PRESSURE AND IN THE ABSENCE OF HYDROCARBON, WHEREBY SUBSTANTIALLY ALL THE SODIUM IS REMOVED FROM THE HYDROCARBONS AND THEN PASSING THE HYDROCARBONS OVER BAUXITE AT ELEVATED TEMPERATURE AND PRESSURE AND IN THE PRESENCE OF HYDROGEN, WHEREBY A CONSIDERABLE PROPORTION OF THE VANDIUM IS REMOVED FROM THE HYDROCABRONS.
US33266253 1952-01-31 1953-01-22 Removal of vanadium and sodium from petroleum hydrocarbons Expired - Lifetime US2687985A (en)

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GB261452A GB744045A (en) 1952-01-31 1952-01-31 Improvements relating to the removal of vanadium and sodium from petroleum hydrocarbons

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FR (1) FR1075295A (en)
GB (1) GB744045A (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2764525A (en) * 1952-06-18 1956-09-25 British Petroleum Co Removal of vanadium and/or sodium from petroleum and petroleum products with alumina and iron oxide
US2769758A (en) * 1951-03-20 1956-11-06 British Petroleum Co Removal of sodium and vanadium from petroleum hydrocarbons followed by catalytic desulphurisation of said petroleum hydrocarbons
US2771401A (en) * 1954-08-05 1956-11-20 Exxon Research Engineering Co Desulfurization of crude oil and crude oil fractions
US2862982A (en) * 1954-12-10 1958-12-02 Exxon Research Engineering Co Removal of alkali metals from viscous hydrocarbon liquids
US2891005A (en) * 1955-12-27 1959-06-16 Exxon Research Engineering Co Removal of metal contaminants from high boiling oils
US3546103A (en) * 1969-02-03 1970-12-08 Exxon Research Engineering Co Hydrogenation catalysts on charcoal in guard chamber for removing metals from petroleum residua
US4343693A (en) * 1979-10-01 1982-08-10 Phillips Petroleum Company Method of removing contaminant from a feedstock stream
FR2542754A1 (en) * 1983-03-15 1984-09-21 Raffinage Cie Francaise METHOD OF HYDRODEMETALLIZING HYDROCARBON LOADS AND CATALYST FOR IMPLEMENTING SAID METHOD
US4816138A (en) * 1984-09-14 1989-03-28 Kinetics Technology International B.V. Process for cleaning of toxic waste materials by refining and/or elimination of biologically difficult to degrade halogen, nitrogen and/or sulfur compounds
US20080000809A1 (en) * 2006-06-30 2008-01-03 Hua Wang Membrane method of removing oil-soluble metals from hydrocarbons

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3077449A (en) * 1955-03-25 1963-02-12 Sinclair Research Inc Method of filtering a fuel oil
US2910434A (en) * 1955-05-24 1959-10-27 Texaco Inc Process for removing trace metals with hydrogen and an inert packing material

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1753859A (en) * 1926-01-18 1930-04-08 Gray Processes Corp Treatment of fluids with solid substances
US2340939A (en) * 1942-06-06 1944-02-08 Standard Oil Dev Co Refining of mineral oils
US2419029A (en) * 1941-04-11 1947-04-15 Phillips Petroleum Co Process for desulfurizing and reforming hydrocarbons
US2614068A (en) * 1952-10-14 Multiunit catalytic cracking

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2614068A (en) * 1952-10-14 Multiunit catalytic cracking
US1753859A (en) * 1926-01-18 1930-04-08 Gray Processes Corp Treatment of fluids with solid substances
US2419029A (en) * 1941-04-11 1947-04-15 Phillips Petroleum Co Process for desulfurizing and reforming hydrocarbons
US2340939A (en) * 1942-06-06 1944-02-08 Standard Oil Dev Co Refining of mineral oils

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2769758A (en) * 1951-03-20 1956-11-06 British Petroleum Co Removal of sodium and vanadium from petroleum hydrocarbons followed by catalytic desulphurisation of said petroleum hydrocarbons
US2764525A (en) * 1952-06-18 1956-09-25 British Petroleum Co Removal of vanadium and/or sodium from petroleum and petroleum products with alumina and iron oxide
US2771401A (en) * 1954-08-05 1956-11-20 Exxon Research Engineering Co Desulfurization of crude oil and crude oil fractions
US2862982A (en) * 1954-12-10 1958-12-02 Exxon Research Engineering Co Removal of alkali metals from viscous hydrocarbon liquids
US2891005A (en) * 1955-12-27 1959-06-16 Exxon Research Engineering Co Removal of metal contaminants from high boiling oils
US3546103A (en) * 1969-02-03 1970-12-08 Exxon Research Engineering Co Hydrogenation catalysts on charcoal in guard chamber for removing metals from petroleum residua
US4343693A (en) * 1979-10-01 1982-08-10 Phillips Petroleum Company Method of removing contaminant from a feedstock stream
FR2542754A1 (en) * 1983-03-15 1984-09-21 Raffinage Cie Francaise METHOD OF HYDRODEMETALLIZING HYDROCARBON LOADS AND CATALYST FOR IMPLEMENTING SAID METHOD
US4816138A (en) * 1984-09-14 1989-03-28 Kinetics Technology International B.V. Process for cleaning of toxic waste materials by refining and/or elimination of biologically difficult to degrade halogen, nitrogen and/or sulfur compounds
US20080000809A1 (en) * 2006-06-30 2008-01-03 Hua Wang Membrane method of removing oil-soluble metals from hydrocarbons

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BE517222A (en) 1900-01-01
FR1075295A (en) 1954-10-14
GB744045A (en) 1956-02-01
DE959579C (en) 1957-03-07

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