US2383972A - Recovery of vanadim and nickel from petroleum - Google Patents
Recovery of vanadim and nickel from petroleum Download PDFInfo
- Publication number
- US2383972A US2383972A US340016A US34001640A US2383972A US 2383972 A US2383972 A US 2383972A US 340016 A US340016 A US 340016A US 34001640 A US34001640 A US 34001640A US 2383972 A US2383972 A US 2383972A
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- US
- United States
- Prior art keywords
- zeolite
- oil
- vanadium
- constituents
- petroleum
- 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.)
- Expired - Lifetime
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- 239000003208 petroleum Substances 0.000 title description 12
- 238000011084 recovery Methods 0.000 title description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 6
- 229910052759 nickel Inorganic materials 0.000 title description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 28
- 239000010457 zeolite Substances 0.000 description 28
- 239000000470 constituent Substances 0.000 description 25
- 239000003921 oil Substances 0.000 description 20
- 229910052720 vanadium Inorganic materials 0.000 description 20
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 20
- 239000003153 chemical reaction reagent Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000002480 mineral oil Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- -1 alkali metal salts Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 239000011269 tar Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000010763 heavy fuel oil Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229940001593 sodium carbonate Drugs 0.000 description 3
- 239000002641 tar oil Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000765309 Vanadis Species 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
- C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/12—Recovery of used adsorbent
-
- 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
Definitions
- Tar or heavy fuel oil containing the zeolite and the metallic constituents is removed from the bottom of evaporator 9 by means of line 32 and passed through temperature control unit 33.
- the heavy oil fraction is withdrawn from. the temperature control unit a and passed into separator 34 which may commeans of ther characterized in that the reagent will not prise any suitable number of units of any desired design, in which the zeolite is separated from the heavy fuel oil or tar fraction.
- the tar or fuel oil fraction is withdrawn from the system by means of line it and handled in any manner desired.
- the zeolite containing the metallic constituents is withdrawn from separator 34 which may comprise a metallic screen filter by meansof line '30 and handled to remove and recover the metallic constituents from the zeolite by suitable means.
- the zeolite substantially free of oily constituents is withdrawn from washing unit 50 by means of line 53 and handled in a manner to remove and recover the metallic constituents from the zeolite.
- Solvents of this class are for example various diluted solutions of mineral acids as for example sulfuric, hydrochloric and nitric acid.
- the zeolite, free of recovered metallic constituents, is removed from recovery unit 31 by means of line 30, regenerated, and recycled to the system.
- the reagent becomes a hydrogen 'zeolite and it is treated with a brine suchas a sodium chloride brine to regenerate the zeolite and form the sodium zeolite.
- a brine suchas a sodium chloride brine
- the solution of recovered metallic constituents is removed from unit 31. by meansof line I! andpassed to solvent recovery unit I! in which the solutions are handled in a manner to recover the metallic constituents.
- the solvent as desired, may be recycled to the recovery unit by means of line Iii, while the recovered metallic constituents may be withdrawn from the system by means of line H.
- the process of the invention may be widely varied.
- the invention is concerned with a process adapted to the recovery of metallic constituents of the class consisting of molybdenum, vanadium, nickel and zinc from mineral oils, particularly from petroleum oils containing affect the normal refining operation.
- Suitable solid reagents are for example (1) mixtures of sodiumcarbonate and various clays such as kaolin, (2) zirconium oxide, (3) kaolin alumina mixtures, (4) diatomaceous earths, (5) alkali metal salts such as sodium carbonate and potassium carbonate, and (6) the salts of iron and lead which form lead vanadates and ferric vanadates and the like.
- a particularly desirable material comprises molten sulfur which precipitates out of the tar along with the vanadium upon cooling.
- thepreferred solid reagents are selectedfrom the class of alkali metal aluminum silicates of the zeolite type, especially the naturally occurring hydrated alkali metal aluminum silicates, as for example a naturally occurring hydrated sodium aluminum silicate having the formula Nfl-HsAlSlOr.
- the temperatures and pressures will be a function of the characteristics of the particular; feed oil, and will also depend upon the concentration of themetallic compounds present as well as upon the type of reagent employed.
- the temperature and pressure conditions are generally in the range at which substantially no decomposition of the oil occurs due to the efiect of the zeolite.
- the temperatures are in the range from about 250 to 800 ll, but higher temperatures in the range above about 1000 F., are preferred and the pressures vary from atmospheric to oil cracking pressures. It is preferred that the pressures be in the range from about to 1000 lbs/sq. in.
- the metallic constituent may be recovered from the product resulting from the reaction with the reagent by processes essentially involved in solvent treatment or roasting. For example, if
- the vanadium may be recovered from the sulfide by roasting to produce the vanadium oxide and then reduced to substantially pure vanadium by a selective furnace roasting'reaction.
- Ii zeolite be employed the vanadium is extracted by solvent treating the zeolite wltha strong mineral acid as for example a strong solution of hydrochloric or sulfuric acid.
- the vanadium is precipitated from the acid solution preferably as ammonium vanadate by evaporating the acid solution with an excess of ammonium chloride. 7
- the ammonium vanedate is then'roasted to produce the oxide which may be reduced by means of an electric furnace.
- the solid absorbent containing the recovered the vanadium present Upon withdrawal of the tar, the reagent is allowed to settle while the tar is still hot and limpi The reagent is removed and again employed for the recovery of vanadium inthe manner described,
- the solvent employed for removing the occluded tarry oil fractions from the solid absorbent containing the vanadi um after separation from the tarry fraction is preferably a relatively low boiling petroleum oil fraction.
- a particularly desirable solvent comprises a petroleum oil fraction boiling in the range from about 300 F. to 450 F. Under certain operations it may be desirable to remove the tarry fractions from the absorbent by burning.
- Example 1 A feed oil representing the highest 8% boiling fraction of a Lake Venezuela, crude oil was passed over pumice at a temperature of about 900 F., at a velocity of about 23 feet per second. Analysis of the treated oil after 4800 units were treated indicated that substantially complete removal of the vanadium from the oil wassecured and that the vanadium content of the pumice was about 0.24%.
- Example 2 A reduced Venezuela Lagunillas crude was passed over a mixture comprising 50% sodium carbonate and 50% kaolin at a temperature of about 780 F. to 820 F. and at atmospheric pres- Sure.
- the feed rate employed was 1.2 volumes of oil per volume of. catalyst per hour.
- At thetallic constituents of the class consisting of molybdenum, vanadium, nickel and zinc from petroleum oils containing the same, and for the production of relatively higher and relatively lower boiling petroleum oil constituents by cracking which comprises mixing the said petroleum oil with a solid reagent selected from the class of naturally occurring hydrated alkali metal aluminum silicates of the zeolite type, passing the feed oil through heating means adapted to raise the oil to the desired cracking temperature and pressure level, maintaining the feed oil under the desired conditions for the optimum time period, then passing the same through a pressure release valve into an evaporator adapted to concentrate a relatively small quantity of the relatively higher boiling constituents, removing the relatively higher boiling constituents along with the solid reagent containing the desired metallic constituents from the bottom of said evaporator, physically separating the relatively higher boiling constituents from the solid reagent containing the metallic constituents, and recovering the metallic constituents therefrom.
- a solid reagent selected from the class of naturally occurring hydrated alkali metal aluminum silicates of the zeo
- Process for the separation and recovery of vanadium from petroleum oils containing the same and for the production of relatively higher and relatively lower boiling petroleum oil constituents which comprises mixing the feed petroleum oil with a solid reagent selected from the class of alkali metal aluminum silicates of the zeolite type, which will react with the vanadium and which will not substantially afiect the refining operation, passing the feed oil through heating means adapted to raise the oil to the desired cracking temperature and pressure level, maintaining the feed oil under the desired conditions for the optimum time period, then passing the oil through a. pressure release valve into an evaporator adapted to concentrate a relatively small quantity of the relatively higher boiling constituents, removing the relatively higher boiling constituents along with the zeolite containing the vanadium, and recovering the vanadium therefrom.
- a solid reagent selected from the class of alkali metal aluminum silicates of the zeolite type, which will react with the vanadium and which will not substantially afiect the refining operation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Description
Sept. 4, 1945. M. c. K. JONES 2,383,972
RECOVERY OF VANADIUM AND NICKEL FROM PETROLEUM Filed June 12, 1940 $CON.DARY BUBBLE TOM/7? 7%? mm Y Zuzana rowa EVAPORA TOR 7 P526 TORE.
CON TRol.
CL 7254 NT UNIT f f/EA w/vc co IL gm i ri w r j i is w r brac sa tg s a metaiu stantially coifiblgtely p11; contagmng t fich 9 .9 ils controllii to produceafi overhead distillate of the desired and point. This distillate is removed boiling range, are removed from the bottomof secondary bubble tower i2. passed through cooler i8, and withdrawn from the system by line 20.
Tar or heavy fuel oil containing the zeolite and the metallic constituents is removed from the bottom of evaporator 9 by means of line 32 and passed through temperature control unit 33. in
which it is possible to either raise or lower the temperature of the tar or heavy fuel oil fraction to the desired degree. The heavy oil fraction is withdrawn from. the temperature control unit a and passed into separator 34 which may commeans of ther characterized in that the reagent will not prise any suitable number of units of any desired design, in which the zeolite is separated from the heavy fuel oil or tar fraction. The tar or fuel oil fraction is withdrawn from the system by means of line it and handled in any manner desired. The zeolite containing the metallic constituents is withdrawn from separator 34 which may comprise a metallic screen filter by meansof line '30 and handled to remove and recover the metallic constituents from the zeolite by suitable means. This is preferably accomplished by passing the zeolite to a solvent washing unit 50 in which the tarry oil fractions are removed from the zeolite by washing with a solvent which is introduced by means of line It and withdrawn by means of line 52.. The zeolite substantially free of oily constituents is withdrawn from washing unit 50 by means of line 53 and handled in a manner to remove and recover the metallic constituents from the zeolite. This is preferably accomplished by treating the zeolite with a solvent having the ability to partially dissolve the metallic constituents from the zeolite. Solvents of this class are for example various diluted solutions of mineral acids as for example sulfuric, hydrochloric and nitric acid. The zeolite, free of recovered metallic constituents, is removed from recovery unit 31 by means of line 30, regenerated, and recycled to the system. Following the acid treatment, the reagent becomes a hydrogen 'zeolite and it is treated with a brine suchas a sodium chloride brine to regenerate the zeolite and form the sodium zeolite. Although the step of regenerating the reagent may be employed in applicant's novel process and forms a valuable adjunct thereto. it is not per se novel. The solution of recovered metallic constituents is removed from unit 31. by meansof line I! andpassed to solvent recovery unit I! in which the solutions are handled in a manner to recover the metallic constituents. The solvent, as desired, may be recycled to the recovery unit by means of line Iii, while the recovered metallic constituents may be withdrawn from the system by means of line H.
The process of the invention may be widely varied. In general the invention is concerned with a process adapted to the recovery of metallic constituents of the class consisting of molybdenum, vanadium, nickel and zinc from mineral oils, particularly from petroleum oils containing affect the normal refining operation. Suitable solid reagents are for example (1) mixtures of sodiumcarbonate and various clays such as kaolin, (2) zirconium oxide, (3) kaolin alumina mixtures, (4) diatomaceous earths, (5) alkali metal salts such as sodium carbonate and potassium carbonate, and (6) the salts of iron and lead which form lead vanadates and ferric vanadates and the like. A particularly desirable material comprises molten sulfur which precipitates out of the tar along with the vanadium upon cooling. However, in general thepreferred solid reagents are selectedfrom the class of alkali metal aluminum silicates of the zeolite type, especially the naturally occurring hydrated alkali metal aluminum silicates, as for example a naturally occurring hydrated sodium aluminum silicate having the formula Nfl-HsAlSlOr.
The temperatures and pressures will be a function of the characteristics of the particular; feed oil, and will also depend upon the concentration of themetallic compounds present as well as upon the type of reagent employed. Whenutilizing a zeolite, the temperature and pressure conditions are generally in the range at which substantially no decomposition of the oil occurs due to the efiect of the zeolite. In general the temperatures are in the range from about 250 to 800 ll, but higher temperatures in the range above about 1000 F., are preferred and the pressures vary from atmospheric to oil cracking pressures. It is preferred that the pressures be in the range from about to 1000 lbs/sq. in.
, The metallic constituent may be recovered from the product resulting from the reaction with the reagent by processes essentially involved in solvent treatment or roasting. For example, if
sulfur be used as the reagent, the vanadium may be recovered from the sulfide by roasting to produce the vanadium oxide and then reduced to substantially pure vanadium by a selective furnace roasting'reaction. Ii zeolite be employed, the vanadium is extracted by solvent treating the zeolite wltha strong mineral acid as for example a strong solution of hydrochloric or sulfuric acid. The vanadium is precipitated from the acid solution preferably as ammonium vanadate by evaporating the acid solution with an excess of ammonium chloride. 7 The ammonium vanedate is then'roasted to produce the oxide which may be reduced by means of an electric furnace.
The solid absorbent containing the recovered the vanadium present. Upon withdrawal of the tar, the reagent is allowed to settle while the tar is still hot and limpi The reagent is removed and again employed for the recovery of vanadium inthe manner described, The solvent employed for removing the occluded tarry oil fractions from the solid absorbent containing the vanadi um after separation from the tarry fraction is preferably a relatively low boiling petroleum oil fraction. A particularly desirable solvent comprises a petroleum oil fraction boiling in the range from about 300 F. to 450 F. Under certain operations it may be desirable to remove the tarry fractions from the absorbent by burning.
In order to more fully illustrate the invention, the following examples are given which should not be construed to restrict the same in any manner whatsoever.
Example 1 A feed oil representing the highest 8% boiling fraction of a Lake Venezuela, crude oil was passed over pumice at a temperature of about 900 F., at a velocity of about 23 feet per second. Analysis of the treated oil after 4800 units were treated indicated that substantially complete removal of the vanadium from the oil wassecured and that the vanadium content of the pumice was about 0.24%.
Example 2 A reduced Venezuela Lagunillas crude was passed over a mixture comprising 50% sodium carbonate and 50% kaolin at a temperature of about 780 F. to 820 F. and at atmospheric pres- Sure. The feed rate employed was 1.2 volumes of oil per volume of. catalyst per hour. At thetallic constituents of the class consisting of molybdenum, vanadium, nickel and zinc from petroleum oils containing the same, and for the production of relatively higher and relatively lower boiling petroleum oil constituents by cracking, which comprises mixing the said petroleum oil with a solid reagent selected from the class of naturally occurring hydrated alkali metal aluminum silicates of the zeolite type, passing the feed oil through heating means adapted to raise the oil to the desired cracking temperature and pressure level, maintaining the feed oil under the desired conditions for the optimum time period, then passing the same through a pressure release valve into an evaporator adapted to concentrate a relatively small quantity of the relatively higher boiling constituents, removing the relatively higher boiling constituents along with the solid reagent containing the desired metallic constituents from the bottom of said evaporator, physically separating the relatively higher boiling constituents from the solid reagent containing the metallic constituents, and recovering the metallic constituents therefrom.
2. Process for the separation and recovery of vanadium from petroleum oils containing the same and for the production of relatively higher and relatively lower boiling petroleum oil constituents which comprises mixing the feed petroleum oil with a solid reagent selected from the class of alkali metal aluminum silicates of the zeolite type, which will react with the vanadium and which will not substantially afiect the refining operation, passing the feed oil through heating means adapted to raise the oil to the desired cracking temperature and pressure level, maintaining the feed oil under the desired conditions for the optimum time period, then passing the oil through a. pressure release valve into an evaporator adapted to concentrate a relatively small quantity of the relatively higher boiling constituents, removing the relatively higher boiling constituents along with the zeolite containing the vanadium, and recovering the vanadium therefrom.
3. Process for the separation and recovery of vanadium from mineral oils containing the same which comprises contactingthe feed mineral oil with an alkali metal aluminum silicate of the zeolite type at an elevated temperature and pressure, which deposits a coating of relatively high boiling mineral oil constituents upon the zeolite, separating the zeolite from the mineral oil, treating the zeolite with a relatively low boiling petroleum oi1 solvent to remove relatively high boiling mineral oil constituents therefrom, separating the zeolite containing the vanadium and recovering the vanadium therefrom.
4. A process according to claim 3 wherein the separated zeolite type reagent is regenerated and recycled to the oil treating step for removal of additional amounts of vanadium from fresh mineral oils.
MINOR C. K. JONES.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US340016A US2383972A (en) | 1940-06-12 | 1940-06-12 | Recovery of vanadim and nickel from petroleum |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US340016A US2383972A (en) | 1940-06-12 | 1940-06-12 | Recovery of vanadim and nickel from petroleum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2383972A true US2383972A (en) | 1945-09-04 |
Family
ID=23331525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US340016A Expired - Lifetime US2383972A (en) | 1940-06-12 | 1940-06-12 | Recovery of vanadim and nickel from petroleum |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2383972A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2683683A (en) * | 1951-04-06 | 1954-07-13 | Houdry Process Corp | Purification of oils |
| US2758060A (en) * | 1951-01-15 | 1956-08-07 | British Petroleum Co | Removal of vanadium and/or sodium from petroleum by hydrogenation in the presence of bauxite |
| 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 |
| US3522001A (en) * | 1968-01-22 | 1970-07-28 | Universal Oil Prod Co | Recovery of metals from carbonaceous material |
| US4110398A (en) * | 1977-04-08 | 1978-08-29 | Uop Inc. | Metal separation from dragstream material of refining process |
| US4420464A (en) * | 1981-10-26 | 1983-12-13 | Rockwell International Corporation | Recovery of vanadium from carbonaceous materials |
| US4437980A (en) | 1982-07-30 | 1984-03-20 | Rockwell International Corporation | Molten salt hydrotreatment process |
-
1940
- 1940-06-12 US US340016A patent/US2383972A/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2758060A (en) * | 1951-01-15 | 1956-08-07 | British Petroleum Co | Removal of vanadium and/or sodium from petroleum by hydrogenation in the presence of bauxite |
| 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 |
| US2683683A (en) * | 1951-04-06 | 1954-07-13 | Houdry Process Corp | Purification of oils |
| 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 |
| US3522001A (en) * | 1968-01-22 | 1970-07-28 | Universal Oil Prod Co | Recovery of metals from carbonaceous material |
| US4110398A (en) * | 1977-04-08 | 1978-08-29 | Uop Inc. | Metal separation from dragstream material of refining process |
| US4420464A (en) * | 1981-10-26 | 1983-12-13 | Rockwell International Corporation | Recovery of vanadium from carbonaceous materials |
| US4437980A (en) | 1982-07-30 | 1984-03-20 | Rockwell International Corporation | Molten salt hydrotreatment process |
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