US3468790A - Process for metal removal from petroleum residues - Google Patents

Process for metal removal from petroleum residues Download PDF

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Publication number
US3468790A
US3468790A US712088A US3468790DA US3468790A US 3468790 A US3468790 A US 3468790A US 712088 A US712088 A US 712088A US 3468790D A US3468790D A US 3468790DA US 3468790 A US3468790 A US 3468790A
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United States
Prior art keywords
solvent
antisolvent
petroleum
ether
residue
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US712088A
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English (en)
Inventor
Andre Deschamps
Philippe Renault
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • 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
    • 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
    • C10G21/003—Solvent de-asphalting

Definitions

  • An object of the process according to this invention is to remove mineral impurities from the crude petroleum and fractions thereof after reduction of the same.
  • metal porphyrines are extracted by means of Z-pyrrolidone or one of the derivatives thereof.
  • the petroleum cut is mixed with Z-pyrrolidone and the mixture is decanted. Two phases are separated.
  • the lower layer consisting of the pyrrolidone containing a part of the metal impurities dissolved therein, together with hydrocarbons of the cut, forms the extract.
  • the higher hydrocarbon layer constitutes the rafiinate.
  • the solvent used is costly. It can be used in smaller amounts, if diluted with a cheap alcohol but the maximal alcohol proportion is 50% and practically comprised between 20 and 25%.
  • An object of the present invention is, at the opposite of the preceding technique, to extract the major part of the hydrocarbons without carrying along therewith the metal impurities, which are thus concentrated in a fraction which corresponds to only a small percentage of the starting reduced crude petroleum.
  • the demetalization process, object of this invention may be carried out according to one of the two following methods:
  • the petroleum cut to be purified is contacted with a solvent such as hereunder defined in which the hydrocarbon cut is dissolved. Thereafter is added an antisolvent which will be also defined hereinafter; this second liquid causes the separation of the major part of metal impurities which are in the form of solid conglomerates carrying along therewith a small part of the hydrocarbon cut and of the mixture solvent+ antisolvent.
  • the major part of the hydrocarbon cut, substantially free from metals (and other impurities) remains dissolved in the mixture solvents-antisolvent.
  • solvent a hydrocarbon ether, linear or cyclic, saturated or not, having from 3 to 12 and preferably from 4 to 7 carbon atoms, said solvent containing from 1 to 3 ether functions in the molecule.
  • solvents methylethyl-ether, diethylether, ethyl-propylether, dipropylether, ethyl-butylether, vinylbutylether, dibutylether, 1,3-dioxane, 1,4-dioxane, 4,4-dimethyl-1,3-dioxane, 1,3-dioxolane, Z-methyl, 1,3-dioxolane, tetrahydrofuran.
  • Cyclic saturated ethers and more particularly tetrahydrofuran are preferred.
  • the second method for carrying out the invention which constitutes the preferred one, consists of contacting the hydrocarbon cut to be purified with a bifunctional organic compound, i.e. a liquid organic compound containing at least one ether function (preferably from 1 to 5) and at least one alcohol function (preferably from 1 to 5), said bifunctional compound having from 3 to 40 carbon atoms and preferably from 4 to 10 carbon atoms and being either linear or cyclic, saturated or not.
  • a bifunctional organic compound i.e. a liquid organic compound containing at least one ether function (preferably from 1 to 5) and at least one alcohol function (preferably from 1 to 5), said bifunctional compound having from 3 to 40 carbon atoms and preferably from 4 to 10 carbon atoms and being either linear or cyclic, saturated or not.
  • diethyleneglycol triethyleneglycol and their higher homologs, diethyleneglycol monoethyl ether, glycerol diethyl ethers, 2(hydroxy-methyl) tetra-hydrofuran, dipropyleneglycol, tetrapropyleneglycol.
  • the bifunctional compound may be used either alone or in admixture with one or more sol-vents and/ or antisolvents as hereabove defined.
  • a solvent or an antisolvent When to the bifunctional compound is associated a solvent or an antisolvent, the latter will be used in an amount of from 0.01 to 0.5 and preferably from 0.05 to 0.2 times the volume of the bifunctional compound.
  • the demetalization treatment according to the two above defined methods can be applied either to reduced crude oils, i.e. to residues of distillation under a pressure close to the atmospheric pressure or to the products obtained by fractionating these atmospheric residues, for instance to cuts obtained by vacuum distillation of atmospheric residues.
  • the residue from vacuum distillation may also, if not too viscous, be purified according to the process of this invention. From a general point of view the charge subjected to the treatment of this invention will have an initial boiling point higher than 250 C. under a pressure of 76 cm. of Hg.
  • the term of petroleum residue being understood that this term may involve the above-defined hydrocarbon cuts.
  • the contact between the petroleum residue and the couple solvent-antisolvent or the bifunctional compound may be achieved into a conventional apparatus such as an agitated tank or an extraction column operated with countercurrent.
  • a conventional apparatus such as an agitated tank or an extraction column operated with countercurrent.
  • the contact temperature may vary Within wide limits, for instance between 20 and 150 C. and preferably between 30 and 80 C.
  • the two-obtained phases are separated and the solvents recovered therefrom by any conventional means such as distillation, washing with water, distillation with steam.
  • the fraction which contains the most part of the organo-metallic compounds also contains asphaltenes, resins and is moreover enriched with sulfur and nitrogen compounds.
  • the process of demetalization object of this invention may therefore be used for deasphalting petroleum residues.
  • Example 2 Example 1 is repeated with 1 kg. of atmospheric residue from Safaniya crude, containing 78 p.p.m. of vanadium and 28 p.p.m. of nickel. There are used 3 kg. of bifunctional compound consisting of 2-butoxy ethanol. The metal impurities precipitate as soon as the residue is contacted with the bifunctional compound. The following operations are the same as in Example 1. There are obtained 0.76 kg. of a residue containing only 15 p.p.m. of vanadium and 3 p.p.m. of nickel, which can be used as fuel.
  • Example 3 Example 2 is repeated with 1 kg. of residue from Safaniya crude, containing 78 p.p.m. of vanadium and 28 p.p.m. of nickel (the same as in preceding example), which is contacted, at ambient temperature, with a mixture of 2 kg. of 2-butoxy ethanol with 0.16 kg. of 95% ethyl alcohol. After recovery of the solvents as precedingly, there are obtained 0.8 kg. of a fuel having only a 15 p.p.m. vanadium content and a 3 p.p.m. nickel content.
  • Example 4 Example 1 is repeated with the same charge (1 kg. of Kuwait atmospheric residue) which is first contacted with 3 kg. of 1-4 dioxane and thereafter with 0.4 kg. of water.
  • Example 5 By repeating Example 1 with the same charge and under the same conditions btu with the use as solvent of 2 kg. of isopropyl ether, and as antisolvent of 1.5 kg. of 95% ethyl alcohol, there are recovered 0.85 kg. of a fuel containing 8 p.p.m. of vanadium and 4 p.p.m. of nickel.
  • Example 6 Example 3 is repeated with the same charge and in the same operating conditions but with the use of a mixture of 2 kg. of 2-ethoxy ethanol and 0.3 kg. of tetrahydrofuran, these two compounds being simultaneously brought into contact with the residue.
  • Ethylene-glycol n-butyl mono-ether 75 Recycled petroleum residue 1O Heptane Water 5 Into the mixer 1 are formed two phases: a heavy phase containing the major part of the metal impurities and the asphaltenes, which is discharged through duct 9, and a lighter phase consisting essentially of demetalized petroleum residue dissolvedin 2-butoxy ethanol, which is conveyed through duct 10 to the separator 2. The separator is also fed with a water stream, introduced through duct 11, and the object of which will be defined hereunder.
  • the heavy phase issued from the mixer 1 is subjected into apparatus 4 to a distillation with steam so as to extract 2-butoxy ethanol and heptane, which are both conveyed to the decanter 5 after passage through the condenser.
  • the heavy fraction containing metal impurities and substantially free from 2-butoxy ethanol and heptane, is discharged through duct 18.
  • This aqueous phase is conveyed partly to the separator 2 through duct 11 and partly to the boiler 7 through duct 21, this boiler supplying with steam the apparatuses 4 and 6 through ducts 22 and 23.
  • the heptane could be replaced by any other saturated hydrocarbon having for example from 5 to 8 carbon atoms, or by a hydrocarbon cut containing two or more of such saturated hydrocarbons.
  • a process of demetalization of a petroleum fraction consisting essentially of residue of crude petroleum distillation, said residue having a boiling point higher than about 250 C. which comprises contacting the petroleum fraction to be demetalized in the liquid phase with at least one member selected from the group consisting of:
  • a couple solvent-antisolvent wherein the solvent is an ether containing about 3 to 12 carbon atoms and from 1 to 3 ether functions per molecule and the antisolvent is selected from the group consisting of water, alcohols and polyols containing from about 1 to 10 carbon atoms, and
  • a process according to claim 1 using a couple solvent-antisolvent wherein the solvent contains about 4 to 7 carbon atoms per molecule and the antisolvent is selected from the group consisting of alcohols and polyols containing about 1 to 5 carbon atoms in the molecule.
  • a process according to claim 10 wherein the bifunctional compound is used in an amount of about 1 to 4 volumes per volume of the petroleum fraction to be demetalized.
  • a process according to claim 1 wherein the bifunctional compound is 2-butoxy ethanol.
  • the solvent is selected from the group consisting of methyl ethyl ether, diethyl ether, ethyl propyl ether, dipropyl ether, ethyl butyl ether, vinyl ether, dibutyl ether, isopropyl ether, 1,3-dioxane, 1,4-dioxane, 4,4-dimethyl-1,3-dioxane, 1,3- dioxolane, Z-methyl, 1,3-dioxolane and tetrahydrofuran.
  • the antisolvent is selected from the group consisting of ethanol, ethylene glycol, l-propanol, glycerol, l-butanol, 2-butan0l, 1- pentanol and l-heptanol.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US712088A 1967-03-09 1968-03-11 Process for metal removal from petroleum residues Expired - Lifetime US3468790A (en)

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DE (1) DE1645764A1 (en))
FR (1) FR1549196A (en))
GB (1) GB1225185A (en))
NL (1) NL6803323A (en))

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617500A (en) * 1969-01-15 1971-11-02 Atlantic Richfield Co Hydroconversion process utilizing a water-washed asphalt feedstock
US3763036A (en) * 1972-02-07 1973-10-02 Texaco Inc A method of reducing the lead content of a used hydrocarbon lubricating oil by adding methylethyl ketone to separate the resulting mixture into a coagulated insoluble phase
US4518490A (en) * 1984-04-06 1985-05-21 The United States Of America As Represented By The United States Department Of Energy Removal of arsenic compounds from petroliferous liquids

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4305813A (en) * 1978-07-10 1981-12-15 Biuro Projektow I Realizacji Inwestycji Rafinerii Nafty "Bipronaft" Method of extractive purification of residues from crude oil refining and heavy ends thereof
US8092853B2 (en) 2003-12-02 2012-01-10 Purina Mills, Llc Gel based livestock feed, method of manufacture and use

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2761821A (en) * 1952-05-28 1956-09-04 Exxon Research Engineering Co Purification of hydrocarbon oils

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2761821A (en) * 1952-05-28 1956-09-04 Exxon Research Engineering Co Purification of hydrocarbon oils

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617500A (en) * 1969-01-15 1971-11-02 Atlantic Richfield Co Hydroconversion process utilizing a water-washed asphalt feedstock
US3763036A (en) * 1972-02-07 1973-10-02 Texaco Inc A method of reducing the lead content of a used hydrocarbon lubricating oil by adding methylethyl ketone to separate the resulting mixture into a coagulated insoluble phase
US4518490A (en) * 1984-04-06 1985-05-21 The United States Of America As Represented By The United States Department Of Energy Removal of arsenic compounds from petroliferous liquids

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Publication number Publication date
GB1225185A (en)) 1971-03-17
DE1645764A1 (de) 1970-07-16
NL6803323A (en)) 1968-09-10
BE711738A (en)) 1968-07-15
FR1549196A (en)) 1968-12-13

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