Classifications

• • 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

• 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 comprises mixing the feedstock oil with a nonaqueous solution of anhydrous nonpolymeric Group IVb; Group Vb, Group VIb, Group VIIb, the non-noble (iron group) metals of Group VIII, copper, zinc, cadmium and mercury halides (except TiCl 4 or FeCl 3 ) or tetrafluoroborates, complexed with nonaqueous polar solvents under conditions of mild agitation and heating whereby the basic nitrogen compounds exchange with the polar solvent to complex with the above-recited metal halides and metal tetrafluoroborates.
• BNC basic nitrogen compounds
• the preferred halide is bromide, and the preferred polar solvent is methanol.
• the oil is then decanted to separate it from the metal halides: BNC complexes and the decantate washed with a polar solvent, which preferably includes water, 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 anhydrous nonpolymeric metal halide or metal tetrafluoroborate-nonaqueous polar solvent complex can be used as such, or they can be impregnated onto a support material such as silica, alumina, silica-alumina, faujasite, kaolin, carbon, zeolite, coal, vermiculite, etc., and used as supported basic nitrogen compound complexation compositions. These supported materials can be regenerated after use by washing with polar solvents. They recover essentially all of their complexation ability.
• the reaction can be described in terms of the following formula: *
• the 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, USA.
• M is the metal component selected from the group consisting of iron, cobalt, titanium, molybdenum, Group IVb, Group Vb, Group VIb, Group VIIb, the non-noble (iron group) of Group VIII, copper, zinc, cadmium, mercury
• X is a halide selected from the group consisting of chloride, bromide, iodide, or is tetrafluoroborate except that when M is titanium or iron, X cannot be chlorine
• n is the number of X atoms satisfying the valence requirements of.the metal at the oxidation state employed
• Q is the complexed non- aqueous polar solvent
• z is the number of nonaqueous polar solvent molecules
• BNC basic nitrogen compounds.
• M is the metal component selected from the group consisting of iron, cobalt, titanium, molybdenum, Group IVb, Group Vb, Group VIb, Group VIIb, the non-noble (iron group) of Group VIII, copper, zinc, cadmium, mercury;
• X is a halide selected from the group consisting of chloride, bromide, iodide, 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 non- aqueous 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 metal halides or metal tetrafluoroborates.
• the 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. Higher concentrations of metal materials or greater volumes of complex solution are employed for oils more highly contaminated with basic nitrogen compounds.
• 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 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 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 0-20°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.
• metal halide or metal tetrafluoroborate materials complexed with the polar solvents are described, they are identified as being an-. hydrous, 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 insoluble 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 anhydrous, nonpolymeric metal halides are prepared by preparing a solution of nonaqueous polar solvent and halogen, 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 if stored under inert atmospheres.
• the 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 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.
• Example 3 Removal of Compounds Containing Basic Nitrogen From Lube Oils by Methanolated Vanadium Dibromide.
• 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.
• Example 4 Removal of Compounds Containing Basic Nitrogen From Lube Oils by Zinc Dibromide and Copper Bromides.
• 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 bromide 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.
• Example 5 Removal of Compounds Containing Basic Nitrogen From Lube Oils by Manganese, Iron, and Cobalt Bromides.
• Example 6 Methanolated Transition Metal Tetrafluoroborates are Basic Nitrogen Scavengers.
• Example 7 Removal of Compounds Containing Basic Nitrogen From Lube Oils by Silica Gel Impregnated with Ti(III), V(II), Cr(III), Mo(II), Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II) Bromides.
• 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 TiCl 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)

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Citations (3)

• 1982
  • 1982-02-16 EP EP19820300762 patent/EP0086293B1/fr not_active Expired
  • 1982-02-16 DE DE8282300762T patent/DE3270205D1/de not_active Expired

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