EP0086293B1 - Procédé d'élimination sélective de composés azotés basiques d'huiles de graissage en utilisant des halogénures, des tétrafluoroborates et des métaux de transition - Google Patents

Procédé d'élimination sélective de composés azotés basiques d'huiles de graissage en utilisant des halogénures, des tétrafluoroborates et des métaux de transition Download PDF

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Publication number
EP0086293B1
EP0086293B1 EP19820300762 EP82300762A EP0086293B1 EP 0086293 B1 EP0086293 B1 EP 0086293B1 EP 19820300762 EP19820300762 EP 19820300762 EP 82300762 A EP82300762 A EP 82300762A EP 0086293 B1 EP0086293 B1 EP 0086293B1
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European Patent Office
Prior art keywords
metal
polar solvent
group
tetrafluoroborate
bnc
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EP19820300762
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German (de)
English (en)
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EP0086293A1 (fr
Inventor
Jacob Joseph Habeeb
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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Priority to DE8282300762T priority Critical patent/DE3270205D1/de
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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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/06—Metal salts, or metal salts deposited on a carrier
    • C10G29/12—Halides
    • 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

Definitions

  • the present invention relates to a method for the selective removal of basic nitrogen compounds (BNC) from natural and synthetic hydrocarbon feedstocks, preferably petroleum feedstocks, most preferably lube and transformer oils, which method comprises mixing the feedstock oil under conditions of agitation and heating to a temperature in the range of from 25 to 120°C with a nonaqueous solution of (A) an anhydrous nonpolymeric halide (otherthan chloride) of a metal selected from the metals of Group IVb * , Group Vb, Group Vlb, Group Vllb, the non-noble (iron group) metals of Group VIII, copper, zinc, cadmium and mercury, or (B) an anhydrous nonpolymeric tetrafluoroborate of a metal selected from the metals of Group IVb, Group Vb, Group Vlb, Group Vllb, the non-noble metals of Group VIII, copper, zinc, cadmium and mercury, which metal halide or metal tetrafluoroborate is complexed
  • a feedstock of reduced BNC content is separated from the complex of nonaqueous polar solvent with either the metal halide or metal tetrafluoroborate with which the BNC removed from the feedstock are now complexed by their exchange with the polar solvent.
  • the preferred halide is bromide
  • the preferred polar solvent is methanol.
  • the separation of the resulting oil from the complexed BNC and metal halide-nonaqueous polar solvent or metal tetrafluoroborate-nonaqueous polar solvent may be effected in any convenient manner, e.g. by decantation, and the separated oil washed with polar solvent and dried.
  • the basic nitrogen compound-metal halide or metal tetrafluoroborate complex dissolves in the polar solvent, and that which is in the oil is removed by the polar solvent wash.
  • the preferred polar solvent for the wash step is water.
  • the complex of nonaqueous polar solvent with either the anhydrous nonpolymeric metal halide or the anhydrous metal tetrafluoroborate can be used as such, or it can be impregnated onto a support material such as silica, alumina, silica-alumina, faujasite, kaolin, carbon, zeolite, coal, vermiculite, etc., and used as a supported basic nitrogen compound complexation composition. These supported materials can be regenerated after use by washing with polar solvents. They recover essentially all of their complexation ability.
  • M is the metal component selected from the metals of Group IVb, Group Vb, Group Vllb, the non-noble (iron group) metals of Group VIII, copper, zinc, cadmium, mercury;
  • X is either a halide, other than chloride, or is tetrafluoroborate;
  • n is the number of X atoms satisfying the valence requirements of the metal at the oxidation state employed;
  • Q is the complexed nonaqueous polar solvent;
  • z is the number of nonaqueous polar solvent molecules and BNC is basic nitrogen compounds.
  • the metal M is preferably selected from the group consisting of nickel, chromium, vanadium, zinc, copper, manganese, iron, cobalt, titanium, molybdenum, cadmium, and mercury.
  • the preferred halide is bromide.
  • the most preferred metal bromides are chromium tribromide, nickel dibromide, vanadium dibromide, zinc dibromide, and the copper, manganese, iron and cobalt bromides.
  • These metal bromides are preferably complexed with a nonaqueous polar solvent selected from the group consisting of methanol, ethanol, acetone, acetonitrile, most preferably methanol.
  • Any oil which can be benefited by the removal of basic nitrogen compounds can be treated by the method of the instant invention.
  • Natural and synthetic hydrocarbon feedstocks such as those derived from coal, tar sands or oil shale, etc., can thus be processed.
  • Typical of feedstocks which are processed are the petroleum oils destined for use as lubricating or transformer oils wherein the presence of basic nitrogen compounds is known to be a major cause of reduced oxidative stability.
  • These oils need not be pretreated prior to this BNC removal process, since the process functions effectively in the presence of a broad spectrum of contaminants, including, for example, and not by way of limitation, N-methyl pyrrolidone, acids, ionic species, phenols, sulfates, etc.
  • Polar compounds, other than BNC also contribute to the oxidative instability of the oils and these too can be removed by use of the metal solution complexes wherein the polar compounds complex to the said metal halides or metal tetrafluoroborates.
  • Periodic Table groups used in this patent specification are those of the Periodic Table according to "The Handbook of Chemistry and Physics", published by the Chemical Rubber Publishing Company, Cleveland, Ohio, U.S.A. tetrafluoroborate molecule.
  • a stoichiometric amount of the said metal halide or metal tetrafluoroborate (as determined by the metal oxidation state) is employed.
  • the said metal halide or metal tetrafluoroborate is employed in this process in the form of a complex with a nonaqueous polar solvent.
  • concentration of metal halide or metal tetrafluoroborate, which may be effectively employed in the chosen solvent depends upon the choice of metal and is limited solely by the solubility of the metal halide or metal tetrafluoroborate in the solvent. Typically, this ranges anywhere from about 0.1 gram material or less per milliliter-solvent to 1.0 gram material or more per milliliter solvent.
  • the oils and metal solution complexes are mixed so as to obtain high surface contact between the oils and the metal solution complexes. This is typically achieved by mixing under conditions of agitation so as to insure complete mixing of the components and the resultant exchange of BNC with the polar solvent on the said metal halide or metal tetrafluoroborate.
  • This agitation can be achieved by any of a variety of standard methods including mechanical stirring and bubbling gases, preferably inert gases such as N 2 through the oil-metal solution complex combination.
  • oil-metal solution complex combinations are subjected to mild heating on the order of a temperature between about 25 to 120°C, preferably 50 to 100°C, most preferably 50 ⁇ 80°C. This heating is employed so as to facilitate the exchange of the BNC for the polar solvent in the said metal halide or metal tetrafluoroborate as shown in Formula I.
  • the oil and metal solution complex are mixed and heated for a time sufficient to insure substantially complete exchange of the BNC and the polar solvent moiety.
  • the oil is then decanted.
  • the decantate is washed with polar solvent or water to remove any metal halide or metal tetrafluoroborate-BNC complex remaining in the oil. These complexes are soluble in the polar solvent or water.
  • the wash solvent may be employed at any convenient temperature, preferably between Q-20°C.
  • the volume of wash solvent is also, any convenient volume, typically 1-5 volumes was solvent per volume decantate.
  • the oil is dried under any convenient condition.
  • the oil is found to have had its basic nitrogen compound content reduced by at least 90% by the practice of the instant process..
  • the said metal halide or metal tetrafluoroborate materials complexed with the polar solvents are described, they are identified as being anhydrous, nonpolymeric materials; and the polar solvent is identified as being any polar solvent except water.
  • Polymeric materials are to be avoided since their exchangeable sites are very limited and difficult to gain access to. Further, polymeric metal halides are relatively insolubl.e in the solvents employed in the instant invention. Similarly, the presence of water at the exchange site in place of other polar solvents is to be avoided since water is exchanged only with extreme difficulty and only at temperatures high enough to adversely effect the quality of the oil and/or decompose the metal halide (see Table 7).
  • the anhydrous, nonpolymeric metal halides used in the instant invention are prepared by the electrochemical technique explained in detail in "Electrochemical Preparation of Anhydrous Halides of Transition Metals (Mn-Zn)", by J. J. Habeeb, L. Neilson and D. G. Tuck, Inorganic Chemistry 17(2), 306 (1978).
  • the said anhydrous, nonpolymeric metal halides are prepared by preparing a solution of nonaqueous polar solvent and halogen (other than chlorine), immersing a cathode of a material such as platinum, and an anode made of the desired metal in the solution and applying a current.
  • the reaction is typically carried out under an inert atmosphere such as nitrogen. After the reaction is stopped, the excess halogen is vented.
  • Metal halide-polar solvent complexes are quite stable it-stored under inert atmospheres.
  • the said anhydrous, nonpolymeric metal halide and metal tetrafluoroborate-polar solvent complexes can be employed as such in the instant process, or they can be deposited on a suitable inorganic refractory oxide or carbonaceous support and used as a regenerable supported BNC complexation material.
  • Typical support materials include silica, alumina, natural and synthetic zeolites, carbon, faujasite, callcite, coal, etc.; preferably silica, alumina, and zeolites; most preferably silica and alumina.
  • These supported complexes are prepared by mixing the chosen support with a volume of the said metal halide or metal tetrafluoroborate-nonaqueous polar solvent complex, heating the combination at from 50 to 100°C under an inert atmosphere, followed by drying at from 75 to 125°C. The heating and drying steps can be accomplished as a single step. Care is taken not to drive off the complex polar solvent molecules.
  • the dried combination is cooled, preferably in an inert atmosphere or under vacuum.
  • the combination metal loading is not critical but will have a typical metal loading range of from 0.5 to 10% metal. Again, the higher the concentration, the more BNC can be removed employing a given volume of supported complex.
  • the oil is contacted with them as by pouring and the BNC are removed by exchange with the nonaqueous polar solvent complexed with the metal halide or metal tetrafluoroborate.
  • the dried decanted oil had a basic nitrogen content of less than 4 ppm, a reduction of more than 90%.
  • the benefit of removing these basic nitrogen components with CrBr 3 is shown by the fact that the Rotary Bomb Life (ASTM D2112) with 0.06 wt.% 2,6 - ditertiarybutyl - para - cresol increased from 179 minutes for the untreated oil to 282 minutes for the treated oil.
  • the basic process essentially is the injection of vanadium bromide-methanol solution into oil followed by decantation of the oil and then water washing to remove the vanadium bromide complexes of basic nitrogen compounds.
  • the process could also be applied to upgrade heavy crudes.
  • Zinc dibromide in methanol and copper bromides (a mixture of Cu(I) and Cu(II) bromides) in methanol are powerful agents for the removal of these basic nitrogen compounds from a wide variety of lube oils-namely, 60 neutrals, 600 neutrals and raw distillates-by forming water soluble complexes of zinc bromide and copper bromides.
  • the basic process for ZnBr 2 and copper bromrde treating is envisaged to be injection of the metal bromide-methanol solution into the oil followed by water washing to remove metal bromide basic nitrogen complexes.
  • Methanolated transition metal tetrafluoroborates are basic nitrogen scavengers
  • Preparation of the impregnated silica gel was performed as follows. Methanolated complexes of the mentioned transition metal bromides were prepared by electrolysis. Samples of these complexes containing 1 to 3 g of metal were mixed with silica gel (different grades) and heated to 70°C under nitrogen followed by drying at 100°C. The new absorbent was cooled in vacuum.
  • This method has an excellent potential in lube oil processing due to the fact that impregnated silica gel beds can be efficiently regenerated and reused for an indefinite number of cycles.
  • Elemental sulphur concentration was decreased from 0.24 wt.% before treatment to 0.1 wt.% after treatment. This indicates that TiC1 4 is non-selective coordinating compound. Removal of naturally occurring antioxidant sulphur compounds will also have a detrimental effect on oil.

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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)

Claims (10)

1. Procédé pour éliminer des composés azotés basiques (CAB) d'une charge d'alimentation hydrocarbonée naturelle ou synthétique, consistant à mélanger la charge d'alimentation, dans des conditions d'agitation et en chauffant à une température dans la gamme de 25 à 120°C, à une solution non-aqueuse, soit (A) d'un halogénure non-polymère anhydre, autre que le chlorure, d'un métal choisi parmi les métaux du Groupe IVb, du Groupe Vb, du Groupe Vlb, du Groupe Vllb, les métaux non-nobles du Groupe VIII, le cuivre, le zinc, le cadmium et le mercure, soit (B) d'un tétrafluoroborate non-polymère anhydre d'un métal choisi parmi les métaux du Groupe IVb, du Groupe Vb, du Groupe Vlb, du Groupe Vllb, les métaux non-nobles du Groupe VIII, le cuivre, le zinc, le cadmium et le mercure, lequel halogénure métallique ou tétrafluoroborate métallique est complexé avec un solvant polaire non-aqueux, les CAB s'échangeant avec le solvant polaire non-aqueux complexé, et eux-mêmes devenant complexés avec l'halogénure ou le tétrafluoroborate métallique.
2. Procédé selon la revendication 1, comprenant l'étape consistant à séparer une charge d'alimentation ayant une teneur réduite en CAB d'avec le complexe du solvant polaire non-aqueux, soit avec l'halogénure métallique, soit avec le tétrafluoroborate métallique, avec lequel les CAB éliminés de la charge d'alimentation sont maintenant complexés par leur échange avec le solvant polaire.
3. Procédé selon la revendication 2, comprenant l'étape consistant à laver avec le solvant polaire la charge d'alimentation séparée, et à sécher.
4. Procédé selon la revendication 3, dans lequel le lavage au solvant polaire utilise de l'eau en tant que solvant polaire.
5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le solvant polaire non-aqueux est choisi entre le méthanol, l'éthanol, l'acétone et l'acétonitrile.
6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le complexe du solvant polaire non-aqueux avec soit l'halogénure métallique, soit le tétrafluoroborate métallique, est imprégné sur une matière de support.
7. Procédé selon la revendication 6, dans lequel le complexe supporté du solvant polaire non-aqueux, avec soit l'halogénure métallique, soit le tétrafluoroborate métallique, est régénéré après utilisation, par lavage avec un solvant polaire non-aqueux à une température de 25 à 75°C.
8. Procédé selon l'une quelconque des revendications 1 à 7, dans lequel le métal est choisi entre le nickel, le chrome, le vanadium, le zinc, le cuivre, le manganèse, le fer, le cobalt, le titane, le molybdène, le cadmium et le mercure.
9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel l'halogénure métallique est un bromure métallique.
10. Procédé selon la revendication 9, dans lequel le bromure métallique es choisi entre le tribromure de chrome, le dibromure de nickel, le dibromure de vanadium, le dibromure de zinc et les bromures de cuivre, de manganèse, de fer et de cobalt.
EP19820300762 1982-02-16 1982-02-16 Procédé d'élimination sélective de composés azotés basiques d'huiles de graissage en utilisant des halogénures, des tétrafluoroborates et des métaux de transition Expired EP0086293B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8282300762T DE3270205D1 (en) 1982-02-16 1982-02-16 Method for selectively removing basic nitrogen compounds from lube oils using transition metal halides and transition metal tetrafluoroborates
EP19820300762 EP0086293B1 (fr) 1982-02-16 1982-02-16 Procédé d'élimination sélective de composés azotés basiques d'huiles de graissage en utilisant des halogénures, des tétrafluoroborates et des métaux de transition

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EP19820300762 EP0086293B1 (fr) 1982-02-16 1982-02-16 Procédé d'élimination sélective de composés azotés basiques d'huiles de graissage en utilisant des halogénures, des tétrafluoroborates et des métaux de transition

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EP0086293B1 true EP0086293B1 (fr) 1986-04-02

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FR2814172A1 (fr) * 2000-09-19 2002-03-22 Total Raffinage Distribution Procede de deazotation de coupes petrolieres par formation de complexes de transfert de charge
FR2864101B1 (fr) * 2003-12-19 2006-03-17 Total France Procede catalytique de purification des hydrocarbures legers

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IT1007571B (it) * 1973-01-03 1976-10-30 Inst Neftechimicheskogo Sintez Metodo per raffinare petrolio e pro dotti della sua trasformazione pri maria
US4113607A (en) * 1977-03-03 1978-09-12 Chevron Research Company Denitrification process for hydrogenated distillate oils
US4145277A (en) * 1978-06-07 1979-03-20 Chevron Research Company Denitrification by furfural-ferric chloride extraction of a hydrodesulfurized hydrocarbonaceous oil

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EP0086293A1 (fr) 1983-08-24

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