US3788978A - Process for the desulfurization of petroleum oil stocks - Google Patents

Process for the desulfurization of petroleum oil stocks Download PDF

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US3788978A
US3788978A US00256547A US3788978DA US3788978A US 3788978 A US3788978 A US 3788978A US 00256547 A US00256547 A US 00256547A US 3788978D A US3788978D A US 3788978DA US 3788978 A US3788978 A US 3788978A
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sodium
sulfur
oil
salt
alkali metal
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W Lewis
A Welty
R Bearden
R Macmullin
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ExxonMobil Technology and Engineering Co
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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
    • C10G29/02—Non-metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/22—Alkali metal sulfides or polysulfides
    • C01B17/34—Polysulfides of sodium or potassium
    • 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
    • C10G29/04—Metals, or metals deposited on a carrier
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/32—Thermal properties
    • C01P2006/33—Phase transition temperatures
    • C01P2006/34—Melting temperatures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • Low sulfur-content petroleum oil stocks are prepared by contacting a sulfur-containing oil stock with an alkali metal, preferably sodium, or an alkali metal alloy, preferably sodium/lead, to produce a mixture comprising a low sulfur oil and a mixture of alkali metal salts dispersed therein.
  • the mixture of salts in oil is resolved by contacting the same with, preferably, 30-160 mole percent hydrogen sulfide based on total moles of salt in the oil, at a temperature of about 670 F.
  • a salt phase separates from the oil.
  • the salt is blended with a molten sulfur-rich alkali metal polysulfide thereby forming a sulfur-depleted alkali metal polysulfide and liberating hydrogen sulfide.
  • molten sulfur may be used in place of the polysulfide.
  • the sulfur-depleted polysulfide is then decomposed electrolytically to reform alkali metal and a sulfur-rich polysulfide, from which elemental sulfur is recovered.
  • the present invention relates to a process for the desulfurization of sulfur-containing petroleum oil stock. More particularly, the process comprises contacting a sulfur-containing oil stock with an alkali metal or alkali metal alloy.
  • the most practical desulfurization process has been hydrogenation of sulfur-containing oils at elevated pressures and temperatures in the presence of an appropriate catalyst.
  • the process requires the use of hydrogen pressures ranging from about 200 to about 2500 p.s.i.g. and temperatures ranging from about 650 to about 800 F., depending on the nature of the oil to be desulfurized and the amount of sulfur required to be removed.
  • the process is efficient in the case of distillate oil feedstocks and less efficient when used with those containing undistilled oil such as whole crudes or residua. This is due to several factors. First, most of the sulfur in the oils is contained in high molecular weight molecules, and it is difficult for them to diffuse through the catalyst pores to the catalyst surface. Furthermore, once at the surface, it is difficult for the sulfur atoms contained in the molecules to see the catalyst surface. Additionally, the feedstocks may contain large amounts of asphaltenes which tend to form coke deposits under the process conditions on the catalyst surface thereby deactivating the catalyst. Moreover, high boiling organometallic compounds pres- 3,788,978 Patented Jan.
  • the alkali polysulfides preferably the sodium polysulfides meet this requirement.
  • the eutectic is at about Na2S31 with a melting point of about 450 F.
  • the electrolysis of molten sodium polysulfide consumes less electrical energy than electrolyzing molten sodium chloride, the traditional electrolysis salt.
  • the process involves contacting a sulfur-containing petroleum oil stock with a desulfurization agent comprising an alkali metal, such as lithium, sodium, potassium, and the like, preferably sodium, or an alkali metal alloy, preferably sodium/lead, at desulfurization conditions, thereby forming a mixture comprising an oil of diminished sulfur content containing alkali metal salts and contacting at least a portion of said mixture with I-I2S.
  • a desulfurization agent comprising an alkali metal, such as lithium, sodium, potassium, and the like, preferably sodium, or an alkali metal alloy, preferably sodium/lead
  • the alkali metal salts comprise in addition to alkali metal sulfide, by-product alkali metal salts such as organo metal salts, metal oxides, mercaptides, amides and the like.
  • by-product alkali metal salts such as organo metal salts, metal oxides, mercaptides, amides and the like.
  • a preconditioning step for salt recovery at least a portion of the oil-salt mixture (generally in the form of a dispersion of submicron sodium salts in oil) is contacted with HZS in amounts ranging from about 10 to about mole percent, based on the total number of moles of salt present in the mixture, preferably 30 to 60 mole percent.
  • HZS treatment is twofold: (1) at least a portion of the by-produet sodium salts such as sodium oxide, sodium hydroxide and the like are converted to sodium hydrosulde, and (2) submicron salts are agglomerated to yield a macrocrystalline salt phase (preferebaly having a particle size between about 150 and 200 microns) which readily disengages from the oil phase.
  • the salt phase is separated from the oil phase and recovered employing one of several well known commercial techniques, notably filtration or centrifugation.
  • the B2S-treated mixture of salts is then contacted with a sulfur-rich sodium polysulide, desirably in the molten state and preferably represented by the formula, NazSX (where x varies from about 4.0 to 4.9, preferably from about 4.4 to 4.8, most preferably from about 4.5 to 4.7).
  • the contacting results in the formation of a sulfur-depleted sodium polysulide, ⁇ i.e., Na2Sy (where y ranges from about 2.8 to 4.5, preferably from about 3.5 to 4.3, most preferably from about 4.0 to 4.2), desirably at a temperature above the melting point of the resulting polysulde.
  • a sulfur-depleted sodium polysulide ⁇ i.e., Na2Sy (where y ranges from about 2.8 to 4.5, preferably from about 3.5 to 4.3, most preferably from about 4.0 to 4.2)
  • This recovery and conversion method will be hereinafter referred to as Scheme A.
  • the H2S-treated mixture of salts in oil i.e., without salt separation from the oil, can be contacted directly with the molten polysulde (Na2SX) thereby converting at least a portion of the salts in situ to a sulfur-depleted polysulfde, NazSy, which is preferably in a molten state (Scheme B).
  • Na2SX molten polysulde
  • the value of y in the sulfur-depleted polysulde NazSy be in the range of about 2.8 to 3.5 in order to avoid backsuliding of the oil phase by the polysulde.
  • the Na2Sy is subsequently electrolyzed in an electrolytic cell as more fully described below, and sodium is withdrawn therefrom and either alloyed with a molten metal such as lead or tin or introduced directly into the desulfurization zone in undiluted form.
  • a molten metal such as lead or tin
  • an excess amount of HES is added to the sodium sulfide/ oil mixture thereby converting the sodium sulide (and other sodium salts present therein) to sodium hydrosulfide (NaSH).
  • the amount of hydrogen sulde added can range from about 110 mole percent based on the total number of moles of salt present in the oil up to about 400 mole percent, but is preferably used in amounts ranging from about 120 to 160 mole percent.
  • the NaSH is substantially molten and is readily separable from the oil. Thereafter, the NaSH is contacted with either NazStx or sulfur to form NazSy which is electrolyzed to form sodium.
  • the amount of Na2Sx that is required to react with the HzS-treated salt mixture varies and is dependent on the compositions of both the sulfur-rich polysulfide and the sulfur-depleted polysulfide.
  • the reaction of Na2Sx with either NazS or NaSH is thought to proceed as follows:
  • y the number of sulfur atoms in Nagsy .uzthe number of sulfur atoms in NaZSx Knowing the number of moles of NazS and NaSH present in the salt mixture and the values for x and y, the required amount of Nazx can be determined. It is noted that the calculated amounts of Na2Sx are minimum values and that larger quantities may be required depending on the amount of other salts that may be present in the salt mixture which also react with th NaZSx.
  • feedstock from which sulfur is desired to be removed may in theory be used in the instant process.
  • suitable feedstocks include whole crude such as Safaniya crude (Middle East), Lagunillas crude (Venezuelan), or U.S. crudes, residual fractions or any distillate fraction.
  • the subjectprocess is particularly adapted to the desulfurization of whole crude or residua that are difficult to treat by other methods such as hydrodesulfurization.
  • the feedstock may be fed directly to the initial contacting zone for desulfurization without pretreatment, it is desirable to desalt the feed in order to prevent NaCl contamination of the molten polysulide feed to the electrolysis cell.
  • Desalting is a well-established process in the industry.
  • a particularly preferred desalting process involves the addition of a small amount of water to the oil in order to dissolve the salt contained therein, followed by electrical coalescers. The oil is then dehydratedby conventional means known in the industry.
  • the sodium may be used as a dispersion of the pure metal or in the form of a Amolten alloy such as sodium/ lead or sodium/tin.
  • a Amolten alloy such as sodium/ lead or sodium/tin.
  • desirable proportions comprise about 0.3 to about 0.5 g.-atom sodium/0.7 to about 0.5 g.atorn lead, and when using sodium/tin, about 0.2 to 0.3 g.atom sodium/ 0.8 to 0.7 g.atom tin.
  • the contacting of the sodium metal or sodium metal alloy with the sulfur-containing oil is preferably carried out at temperatures and pressures suicient to maintain the bulk of the reactants within the reaction zone in the liquid phase.
  • the reaction temperature will generally be maintained between about 450 and 750 F., preferably 600 to 700 F.
  • the reaction pressure will depend on the feed and temperature employed. For reduced crude fractions the pressure will range between about 10 and p.s.i.g., preferably 40 to 60 p.s.i.g. For whole or topped crude, pressures may be raised to as high as about 500 to 600 p.s.i.g. in order to maintain all or most of the oil in the liquid phase.
  • the sodium metal reacts with the sulfur-containing oil stock as shown in Equation 5 below to yield sodium sulfide which generally forms as a microcrystalline dispersion in the oil.
  • organo-oxygen contained in the feedstock is removed therefrom by reacting with the sodium metal.
  • thiosulfate, hydroxide and salts of organic acids may be formed. (Typical crudes contain between about 0.1 and 0.2% organic oxygen).
  • organo-nitrogen and organo-metals are also removed from the oil by reaction with the sodium.
  • the desulfurization step is conducted as a batch or continuous type operation but is preferably continuous.
  • the various means customarily employed in extraction processes to increase the contact area between the oil stock and the sodium metal or alloy thereof can be employed.
  • the apparatus used in the desulfurization step is of a conventional nature and can comprise a single reactor or mutiple reactors equipped with (a) shed rows or other stationary devices to encourage contacting; (b) bark mixers; (c) eicient stirring devices such as mechanical agitators, jets of restricted internal diameter, turbomxers and the like, or (d) a packed bed.
  • the petroleum oil stock and the sodium metal or sodium metal alloy can be passed through one or more reactors in concurrent, crosscurrent, or countercurrent ow, etc.
  • reaction system is thoroughly purged with dry nitrogen and the feedstock dried prior to introduction into the reaction. It is understood that trace amounts of water, i.e., less than about 0.5 weight percent, preferably less than about 0.1 weight percent based on total feed, can be present in the reactor. Where there are larger amounts of water, process eiciency will ⁇ be lowered somewhat as a consequence of sodium reacting with the water.
  • the resulting oil dispersion is subsequently removed from the desulfurization zone and contacted with HZS as described supra.
  • the NazSy is cycled to electrolytic cells wherein it is dissociated to form molten sodium and a sulfur-rich sodium polysulde, i.e., Na2Sz wherein z ranges from about 4.5 to 5.0, preferably from about 4.6 to 4.9, most preferably from about 4.7 to 4.9.
  • the sodium thereby formed is then withdrawn and either alloyed with a molten metal such as lead or tin or introduced directly into the desulfurization zone in undiluted form as hereinabove described.
  • the electrolytic cell unit will preferably comprise a sodium ion-conducting physical and electronic barrier or membrane that separates alkali metal on the one side from alkali metal polysulde on the other side.
  • the membrane may be composed of any material that can function as a sodium ion-conducting separator; however, beta-alumina containing sodium oxide is preferred.
  • beta-alumina will contain sodium oxide in the general range of about Na20-11Al2O3-Na20'5Al2O3. It is noted that when an alkali metal other than sodium is employed in the instant process, the oxide of the alkali metal will be admixed with the beta-alumina in lieu of NazO.
  • the beta-alumina may be used in the pure form of doped with a small amount of metal oxide such as MgO, LizO and the like.
  • metal oxide such as MgO, LizO and the like.
  • doped betaalumina is provided in an article appearing in the Electrochemical Society -Extended Abstracts-Los Angeles Meeting-May -15, 1970, entitled Ionic Conduction in Impurity Doped ,B-alumina, by Atsuo Imai et al., the disclosure of which is incorporated herein by reference.
  • sodium ions migrate from the sodium polysuliide side, i.e., the anode side, through the barrier to the sodium metal side, i.e., the cathode side, where they are neutralized by electrons.
  • the Sz anions are continually removed from the cell in combined form with sodium, i.e., NagSz.
  • the anode may comprise any suitable electron conducting-current collector such as graphite, molybdenum, titanium, chromium, stainless steel, or aluminum that can withstand corrosive attack of the sodium polysulde.
  • the cells are arranged preferably in series electrically, so that the anode for one cell is the cathode for the one adjacent to it. The overall reaction is shown below:
  • the recovered Na2SZ can be reduced in sulfur content to Na2SX (the latter being contacted with the H2S-treated salt mixture as described supra) by application of a vacuum and/or heat thereby liberating sulfur corresponding to that which was removed from the oil.
  • Na2SZ may be contacted directly with the HzS-treated salt mixture.
  • elemental sulfur is allowed to build up in the cell and the operating temperature therein is maintained high enough so that the sulfur is continuously removed therefrom as vapor.
  • liquid sulfur forms in the cell and is separated from the polysulde outside the cell.
  • liquid sulfur forms in the cells and is separated from i.e., in situ, before the molten sodium metal is withdrawn from the electrolytic cell by continuously feeding lead or spent sodium/ lead alloy to the cathode side of the cell.
  • beta-alumina type cell any other cell that is capable of economically decomposing sodium polysulde into molten sodium is sufficient for the present purposes.
  • a particular beta-alumina electrolytic cell and methods for the preparation of beta-alumina are described in such patents as U.S. 3,488,271 and 3,404,036 to J. T. Kummer et al., U.S. 3,468,709' to J. T. Kummer and U.S. 3,446,677 and U.S. 375,225 to G. T. Tennenhouse, the disclosures of which are incorporated herein by reference.
  • FIG. 1 is a ow diagram of the overall desulfurization process using sodium metal in pure form.
  • Desulfurizagon salts are recovered from the oil according to Scheme FIG. 2 shows the reactor system for desulfurization with an alloy of sodium, i.e., sodium/lead.
  • FIG. 3 shows the changes required to operate the process using salt recovery Scheme B.
  • FIG. 4 shows the steps used in salt recovery Schemes C and D.
  • FIG. 5 is a simplified scheme showing the formation of the molten sodium within the electrolyte cell.
  • the desulfurization reactor systems used in the instant process vary depending on whether sodium or sodium alloy is used as the reactant.
  • the system using sodium will be described rst, then the system using sodium alloy.
  • a sulfur-containing feedstock preheated to 450500 F., is fed by means of line 1 and pump 2 to separator vessel 3 where trace amounts of water and light hydrocarbon fractions are removed through line 4.
  • the feed is then discharged through line 5 by pump 6 to lter vessel 7 wherein particulate matter, i.e., coke, scale, etc., is removed.
  • the feed is preliminarily desalted by conventional means (not shown). Feed exiting the iilter via line 8 is split into two streams. A small portion is fed through line 9 and heat exchanger 14 to dispersator vessel 11 where a dispersion is formed with sodium entering through line 67.
  • the dispersator vessel is of a conventional design and is operated at Z50-300 F. at atmospheric pressure. The vessel is blanketed with nitrogen.
  • the resultant dispersion, drawn thorugh line 12 blends with the balance of the feed in line 10 and enters the ⁇ charging pump 13, Where the pressure is raised to about 500 p.s.i.g., for whole crudes and distillates and about 50 p.s.i.g. for residual fuels.
  • the feedstock will ordinarily be a whole crude of about 1 to about 3 weight percent sulfur based on total feed or a residual stock of about 2 to about 7 weight percent sulfur based on total feed, although distillate stocks can be used.
  • the oil enters heat exchanger 16 via line 15 where the temperature is raised to about 00 to 550 F. and is then fed through line 17 to reactor vessel 18.
  • the reactor contains bafiies 19 to promote continuing contact between sodium and the oil and to prevent bypassing from the inlet to the outlet. Holding time in the reactor is about 15 to 60 minutes and is preferably 30 minutes.
  • the temperature at thertop of reactor 18 is about 680 F. Gas that is formed due to the increase in temperature is taken overhead through line 20 and is condensed and depresf surized by conventional means (not shown).
  • the desulfurized oil containing dispersed sodium sulfide and other salts leaves the top of reactor 18 via line 21.
  • FIG. 1 The remainder of FIG. 1 will be explained below after describing the alternate reactor system for sodium alloy shown in FIG. 2.
  • FIG. 2 shows the reactor system for the case where sodium alloy is used. It differs from the case where sodium alone is used primarily in that oil is recycled to the reactor in order to prevent cooling of the alloy below its melting point and in order to recover and recycle the spent alloy.
  • the feedstock which has been preliminarily preheated, dehydrated and de salted as per FIG. 1 is premixed in line 17 with desulfurized recycled oil from pump 68.
  • the mixed oil stream enters reactor vessel 69 via line 17 and flows in an upward direction therethrough.
  • the vessel is of such a size that the oil remains in the reaction portion below the sodium alloy disperser 70 for about minutes to about l hour.
  • the sodium alloy preferably sodium/lead or sodium/ tin or a mixture of the two, enters reactor 69 via disperser 70.
  • Atom compositions of about 0.3 to 0.5 Nat/0.7 to 0.5 Pb or 0.2 to 0.3 Na/ 0.8 to 0.7 Sn are suitable.
  • the spent alloy collects in the bottom of reactor 69 and passes via line 72 to the alloy storage vessel 73.
  • the alloy is fortified by contact with freshly regenerated sodium entering vessel 73 via line 67.
  • Pump 75 feeds the fortified alloy via line 76 to disperser 70.
  • the dispersed oil passes into a settler zone located in the top of reactor 69 where any small, entrained alloy particles are allowed to settle.
  • Bafes 77 act as collecting plates for the alloy particles and are placed at a slight angle so that the coalesced alloy can run off the ends.
  • the desulfurized oil/sodium sulfide dispersion leaves reactor 69 via line 21.
  • contacting vessel 22 sodium sulfide-oil dispersion in line 21 is introduced into contacting vessel 22 wherein the said dispersion is contacted with 30-80 mole percent hydrogen sulfide based on the total moles of salts contained in the oil, at a ternperature between about 60G-800 lF., preferably 625- 750 F., eg., 700 F., and most preferably at the temperature of the desulfurizaiton step.
  • the pressure is maintained between about 25-50 p.s.i.g. Hydrogen sulfide is introduced into said contactor via line 23. Residence time in the contactor vessel is on the order of about 10 minutes, although longer or shorter times may be used if desired.
  • the H2S-treated dispersion exits through line 24 at about 700 F., and 25-100 p.s.i.g. and is then cooled to about 450 F. in heat exchanger 25.
  • the mixture is then fed through line 26 to hydroclone vessels 27 and 28 in series.
  • Desulfurized oil is withdrawn via line 29 to heat exchanger 30 and exits at Z50-300 F. through line 31.
  • An acid such as dilute sulfuric acid or acetic acid, may be injected into line 31 through line 32 to react with oil soluble sodium salts, eg., sodium mercaptides and the like and the resultant mixture enters the electrostatic precipitator 34 via line 33.
  • the acidic aqueous phase from vessel 34 is withdrawn through line 36 and discarded.
  • Desulfurized oil is fed through line 35 to steam stripper 37 and subsequently to storage via line 38.
  • Oil-salt slurry drawn from the hydroclone vessels through lines 39 and 40 is fed to wash vessel 41 where a light hydrocarbon Wash, entering through line 42, is used to remove heavy adhering oil.
  • the wash eluent is drawn off through line 43 and is eventually fractionated to recover the desulfurized oil content and the light hydrocarbon.
  • the wash vessel operates at 25-100 p.s.i.g. at temperatures of 150-300" F.
  • a slurry of washed solids is fed through line 44 to drier 45 to remove light hydrocarbon, which is taken off through line 46.
  • Dry solids are fed to blending vessel 48 via line 47, wherein contact is made with sulfur rich polysulde (Nazsx as hereinabove described) that enters the vessel through line 49.
  • the contacting is conducted at a temperature of about 500 to 820 F., preferably 600800 F., most preferably from about 650-750 F., e.g., 700 F., and at a pressure between about atmospheric pressure and p.s.i.g., preferably between atmospheric pressure and 50 p.s.i.g.
  • Hydrogen sulfide released in the blending reaction along with some small amount of light hydrocarbon is removed through line 50, blended with makeup hydrogen sulfide entering from line 51 and is recycled to vessel 22 by way of line 23.
  • molten sulfur depleted polysulfide (Na2Sy as hereinabove defined) formed by the reaction of H2S-treated salts with sulfur-rich polysullfide is removed from blending vessel 48 through line 52 and fed to iilter vessel 53 to remove particulate matter such as coke and melt insoluble salts.
  • 'Line 54 is used to purge a small stream of sodium polysullide ⁇ from the system in order to prevent buildup of impurities to an inoperable level.
  • Na2CO3, Na2SO3 and the like may also be present in the polysulfide.
  • these impurities can be removed by treatment with H28, thereby converting at least a portion of the impurities to polysulfide.
  • Treated NazSy is introduced into cell 56 via line 55.
  • the process incorporating salt recovery Scheme B is illustrated by reference to FIG. 3.
  • the hydrogen sulfidetreated oil-salt dispersion removed 'from contactor vessel 22 is fed through line 26 to scrubbing tower 80 wherein it is contacted countercurrently with molten sodium polysulfide (Na-28X) that is introduced via line 95.
  • Na-28X molten sodium polysulfide
  • the tower is divided into a series of stages by foraminous plates 81 and is maintained at a temperature ranging from about 500 to 800 F., preferably 650 to 700 lF., and a pressure ranging from about 50 to 500 p.s.i.g., preferably about 50 to about 100 p.s.i.g.
  • the tower is divided into a series of stages by foraminous plates 81 and is maintained at a temperature ranging from about 500 to 800 F., preferably 650 to 700 lF., and a pressure ranging from about 50 to 500 p.s.i.g., preferably about 50 to about 100 p.s.i.g.
  • the tower is divided into a series of stages by foraminous plates 81 and is maintained at a temperature ranging from about 500 to 800 F., preferably 650 to 700 lF., and a pressure ranging from about 50 to 500 p.s.i.g., preferably about 50 to about 100 p.s.i.g.
  • the apparatus is of a conventional nature and can comprise a single reactor or multiple reactors equippcd with eicient stirring devices such as mechanical agitators, jet of restricted internal diameter, turbomixers and the like.
  • the sodium polysulde, i.e., NaZSX and the oil/sodium sulfide mixture can be passed through one or more reactors in concurrent, crosscurrent or countercurrent flow.
  • the molten sulfur-depleted polysulde (.NaZSy where y varies from 2.8 to 3.5) removed from the tower via line 96 is split into two parts. One portion is fed through line 94 to blend with a portion of the sulfur-rich polysulfide product entering from line 93.
  • the ratio of sulfurrich and sulfur-depleted polysulide will be regulated by the value of x in the desired scrubbing agent, NazSx.
  • the remaining sulfur-depleted polysullide in line 97 is blended with the remaining sulfur-rich polysulfide entering from line 92 and the resultant mixture is fed via line 52 to the electrolytic cells.
  • the process incorporating salt recovery Scheme C is illustrated by reference to FIG. 4.
  • an excess amount (110-160 mole percent based on total salts contained in the oil) of hydrogen sulfide is added to the oil-salt dispersion in vessel 22 at a ternperature of about 670'-800 F., preferably 680-750 F. and at a pressure of about 50-500 p.s.i.g., preferably 100- 200 p.s.i.g.
  • the resultant mixture is then fed via line 26 to the settler vessel 82 which operates at conditions similar to those used in vessel 22. Residence time is on the order of 5 to 30 minutes, preferably about 15 minutes.
  • Molten sodium hydrosulde separates from the oil, collects at the bottom of the settler and is drawn off through line 83 which feeds directly to the polysulde blending vessel 48 as noted in FIG. 1. Subsequent steps are identical to those described in FIG. l.
  • the product oil is withdrawn through line 29 and is processed according to Scheme A of FIG. l.
  • the sodium polysulde product i.e., Na2Sy Withdrawn through line 99
  • Na2Sy Withdrawn is yblended with pyrolyzer polysulde product (NazSX) and fed via line 52 to the electrolytic cells.
  • Liberated hydrogen sulfide is taken overhead through line 50 and is ultimately recycled to contacting vessel 22.
  • the pyrolyzer vessel 60 is operated at conditions rela- 10 tively more severe than those used in Scheme A in order to furnish the volume of sulfur required.
  • a dry nitrogen stream blankets the electrolytic cells.
  • the electrolytic cells may comprise any cell capable of converting the polysuliide to sodium metal.
  • the individual cell unit comprises a molten sodium-containing cavity and a molten sodiu-m polysulfidecontaining cavity separated from each other by a sodium ion-permeable membrane comprising preferably crystalline beta-alumina as already described.
  • FIG. 5 A schematic representation of one embodiment of a cell unit is shown in FIG. 5.
  • the beta-alumina membrane 4 acts both as a physical separator and alkali ion conductor between the two cavities.
  • Sodium polysulfide is introduced into cavity 5 via line 6; it is, by its nature, highly ionized into sodium cations and polysulde anions. The latter are oxidized to elemental sulfur that reacts further to yield sulfur-enriched polysulfide anions.
  • the anions along with the requisite sodium cations are subsequently removed via line 7 from cavity 5 as sulfur-enriched sodium polysulde (Na2Sz where z varies from about 4.5 to 5.0). Electrons which are given up by the polysulde anions flow through the metal separating sheet (current collector) 8, which also serves as the anode to form a complete circuit. Thus the anode for one cell ybecomes the cathode for the next.
  • the cell cavity 5 may be partially or fully filled with a porous or nonporus electron-conducting material such as graphite, molybdenum, titanium, chromium, aluminum, nickel-iron alloys and other alloys and the like.
  • the electrolytic cell 56 comprises a plurality of individual cell units in order to provide a sufcient output of sodium.
  • a plurality of cells e.g., about -200 cells may be operated in series in order to build up the overall voltage to about 280-700 volts.
  • the total amount of cell area required depends on the amount of sodium required, and is in the range of about 20 to 70 square feet per pound per minute of sodium.
  • the temperature in the cell rises to about 700-820 F., depending on the amount of cell area, current density used, the resistance of the cell elements and their condition.
  • the composition of the sodium polysuliide leaving the electrolytic cell can be controlled by the ow rate and the current.
  • the composition is controlled such that by applying a reasonable vacuum (and/or heat 1f desired), sulfur corresponding to that which was removed from the oil can be taken overhead.
  • the sodium polysulde formed in the electrolytic cell is passed via line 57 to surge vessel 58 and then to stripping vessel 60 which is partially evacuated, e.g., to an absolute pressure of about l0 to about 300 mm. Hg, preferably about 50 to 100 mm. Hg, to vaporize some of the sulfur and reduce the sulfur content of the polysulfide so that the final polysulde composition is Na-SX wherein x takes values ranging from about 4.0 t0 about 4.9, preferably about 4.4 to about 4.8.
  • sulfur vapor pressure for example, the composition in equilibrium therewith is approximately Na2s4 32 at 700 F., N32S473 at 750 F., and Na2s4'64 at 800 F.
  • the sulfur vapor is taken overhead through line 61 and condensed by conventional means (not shown). As indicated supra the resulting polysulde is then recycled via line 49 to scrubbing tower 48.
  • at least a 11 portion of the sodium polysulfide stream exiting from the cell can be contacted directly with the HzS-treated salt mixture, thereby by-passing the evacuating operation in vessel 60.
  • Na2S5 exiting from the cell can be contacted directly with the HZS-treated salt mixture.
  • the molten sodium is subsequently removed from the electrolytic cell through a current breaker (not shown) and passed via line 62 to surge vessel 63 where it is blended with makeup sodium entering at line 64 and then fed via line 65, pump 66 and line 67 to vessel 11.
  • the reactor consisted of a standard, one liter Paar autoclave, which was constructed of Monel steel. Two modifications were made, however. An oversized turbine blade stirrer head was substituted for the standard item to aid in lifting and dispersing sodium and its alloys, particularly the alloy with lead. Also, the dipleg was tted with a 50 micron metallic filter element to aid in sampling the oil phase when mixtures of salts and oil were present.
  • the reactor head contained the usual openings and fittings for measurement of pressure and temperature and for the addition of gases.
  • the reactor was charged at room temperature with the desired quantity of sulfur-containing oil and freshly cut sodium. Alternatively, in some runs, S- dium was added as an alloy with lead. The reactor was sealed and thoroughly flushed with nitrogen. About 50 p.s.i.g. of the flush gas was present when heatup was begun. The reactor temperature was brought to approximately 450 F. prior to beginning stirred cotact, thereby minimizing the reaction time below the normal run temperaure range of 60G-700 F.
  • the yield of gaseous products comprising materials lighter than or the same weight as pentane was determined by cooling the reactor to room temperature, venting the gases through a wet test How meter to determine volume and then submitting a representative sample for component analysis by mass spectrometry.
  • Coke formed in the desulfurization reaction was most often recovered with the sodium salts and is reported as the water insoluble fraction of the salt.
  • the reactor was cooled to 200 F. without agitation.
  • the salts formed a solid layer on the reactor bottom and were removed wtih hammer and chisel.
  • the solidified molten layer was subsequently crushed, washed with hydrocarbon and dried.
  • molten sodium polysulfide Na-28x
  • H2S-treated salts Conversion of H2S-treated salts to sodium tetrasullide was accomplished by melting the required amount of sodium pentasuliide (M.P.-485 F.) in the reactor under an atmosphere of dry nitrogen. With the temperature adjusted to 600 F. (above the melting point of endproduct salt), powdered B2S-treated salt was fed in by means of the screw feeder. Hydrogen suliide evolution was instantaneous. Gentle stirring was used to break up solid crusts that formed on the surface from time to time. Upon completing the salt addition, the resultant melt was held for 15 minutes at ⁇ 600" F. to insure complete reaction. A lcontinuous nitrogen sweep was employed to carry the evolved H28 to a sodium hydroxide scrubber. Upon completion of the heating period, the melt was cooled to room temperature, pulverized and stored under nitrogen.
  • M.P.-485 F. sodium pentasuliide
  • Sulfur can be substituted for the sodium pentasulde reactant, in which case the powdered sulfur and H2S- treated salts are premixed and then heated to 600 F. Hydrogen sulfide evolution is rapid beginning at about 400 F. and is complete by the time a homogeneous melt is obtained at 600 F.
  • Electrolysis of sodium tetrasulfide (NagSy) (sodium regenerationproposed technique):
  • the laboratory electrolytic cell consists of a beta-alumina tube sealed into a Pyrex glass reservoir for sodium metal and surrounded by graphite felt packing.
  • the outer shell of stainless steel serves as the anode current collector.
  • the cell has a bottom inlet line and a top outlet line.
  • Molten sodium acts as the cathode current contact.
  • Molten sodium tetrasullide is fed through the bottom inlet line and sodium pentasulde product is withdrawn through the top outlet line just below the sodium reservoir. Since molten sodium acts as the cathode surface, it is necessary to load sodium in the beta-alumina tube prior to startup.
  • sodium pentasulde is charged to the ask and brought to the desired temperature and pressure.
  • a slow nitrogen bleed into the melt is used to regulate the vacuum and to provide stirring.
  • Sulfur vapor swept from the flask is collected in the chilled receiver.
  • the pyrolysis rate and depth of pyrolysis i.e., approach to Na2S4, can be increased by raising the temperature and/or lowering the pressure.
  • Oil product analyses Sodium-treated oil products were analyzed not only for sulfur content, but also for changes in metals content and general physical properties such as API gravity, viscosity and asphaltene content. The oil product obtained from each recovery scheme was filtered hot through a number 2 grade Whatman paper prior to analysis. Also a sample of the filtered oil was always relluxed in toluene with a small amount of acetic acid to decompose any salts that escaped filtration and particularly oil soluble salts such as the sodium mercaptides.
  • Desulfurized oil was decanted from the bomb, leaving a slurry of precipitated salts.
  • the salts were subsequently washed with toluene to remove adhering oil and then dried under vacuum. There was recovered 40.5 g.
  • Desulfurized oil decanted from the salt slurry was combined with oil recovered from the toluene wash used in salt purification and was filtered hot F.) through number 2 grade Whatman paper to remove suspended salts.
  • the sample was then split into two parts, one for direct analysis and the other for treatment with acetic acid, to decompose any submicron sodium salts or oil soluble sodium salts such as might be contained as sodium mercaptides (NaSR).
  • NaSR sodium mercaptides
  • Conversion to sodium tetrasullide was accomplished by blending g. of the salt with 117 g. (0.568 mole) of sodium pentasulfide and heating at 600 F. for 30 minutes. Evolution of hydrogen sulfide began as soon as melting was observed, at about 500 F., and was complete when a homogeneous melt was obtained at 600 F.
  • low pressure hydrogen e.g., less than about 500 p.s.i.g., for example 200 p.s.i.g., may be admitted to the desulfurization zone, if desired, in order to suppress organo metallic salt formation during the sodium-contacting step; this desulfurization embodiment may be used in conjunction with any of Schemes A to D.
  • a process for the desulfurization of a sulfur-containing petroleum oil stock comprising contacting said oil stock with a desulfurization agent comprising an alkali metal or an alloy thereof, at desulfurization conditions, thereby forming a mixture comprising oil of reduced sulfur content containing alkali metal salts dispersed therein and contacting said mixture with H28, thereby disengaging a substantial portion of said alkali metal salts from said oil.
  • a process for the desulfurization of a sulfur-containing petroleum oil stock comprising contacting said oil stock with a desulfurization agent selected from the group consisting of sodium and alloys thereof, at desulfurization conditions, thereby forming a mixture comprising oil containing alkali metal salts, contacting at least a portion of said mixture with H2S thereby forming a mixture comprising an oil phase of reduced sulfur content and a salt phase, contacting the H2S-treated mixture with a sulfurrich sodium polysulde thereby forming a sulfur-depleted sodium polysulde, and, thereafter using at least a portion of said sulfur-depleted sodium polysulde as an electrolyte in an electrolytic cell for the production of sodium.
  • a desulfurization agent selected from the group consisting of sodium and alloys thereof, at desulfurization conditions
  • said electrolytic cell comprises an anodic cavity containing polysuliide anions and a cathodic cavity containing sodium metal, said anodic and cathodic cavities separated by a sodium ion-conducting membrane comprising beta-alumina.
  • a process for the desulfurization of a sulfur-containing petroleum oil stock comprising contacting said oil stock with a desulfurization agent selected from the group consisting of sodium and alloys thereof, at desulfurization conditions, thereby fonming a mixture comprising oil containing alkali metal salts, contacting at least a portion of said mixture with H2S thereby forming a mixture cornprising an oilphase of reduced sulfur content and a salt phase, then separating said salt phase from said oil phase and contacting at least a portion of said salt phase with a sulfur-rich sodium polysulide thereby forming a sulfurdepleted sodium polysulde, and thereafter using at least a portion of said sulfur-depleted sodium polysuliide as an electrolyte in an electrolytic cell for the production of sodium metal.
  • a desulfurization agent selected from the group consisting of sodium and alloys thereof, at desulfurization conditions, thereby fonming a mixture comprising oil containing alkali metal salts, contacting at
  • said electrolytic cell comprises an anodic cavity containing polysullde anions and a cathodic cavity containing sodium metal, said anodic and cathodic cavities separated by a sodium ion-conducting membrane comprising beta-alumina.
  • a process for the desulfurization of a sulfur-containing petroleum oil stock comprising contacting said oil stock with a desulfurization agent selected from the group consisting of sodium and alloys thereof, at desulfurization conditions, thereby forming a mixture comprising oil containing alkali metal salts, contacting at least a portion of said mixture with H2S thereby forming a mixture comprising an oil phase of reduced sulfur content and a salt phase, then separating said salt phase from said oil phase and contacting at least a portion of said salt phase with sulfur thereby forming sodium polysulde, and thereafter using at least a portion of said sodium poly-sulfide as an electrolyte in an electrolytic cell for the production of sodium metal.
  • a desulfurization agent selected from the group consisting of sodium and alloys thereof, at desulfurization conditions
  • said electrolytic cell comprises an anodic cavity containing polysulde anions and a cathodic cavity containing sodium metal, said anodic and cathodic cavities separated by a sodium ion-conducting membrane comprising beta-alumina.

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US3976559A (en) * 1975-04-28 1976-08-24 Exxon Research And Engineering Company Combined catalytic and alkali metal hydrodesulfurization and conversion process
US4003824A (en) * 1975-04-28 1977-01-18 Exxon Research And Engineering Company Desulfurization and hydroconversion of residua with sodium hydride and hydrogen
US4007111A (en) * 1975-04-28 1977-02-08 Exxon Research And Engineering Company Residua desulfurization and hydroconversion with sodamide and hydrogen
US4076613A (en) * 1975-04-28 1978-02-28 Exxon Research & Engineering Co. Combined disulfurization and conversion with alkali metals
US4119528A (en) * 1977-08-01 1978-10-10 Exxon Research & Engineering Co. Hydroconversion of residua with potassium sulfide
US4123350A (en) * 1975-04-28 1978-10-31 Exxon Research & Engineering Co. Process for desulfurization of residua with sodamide-hydrogen and regeneration of sodamide
US4127470A (en) * 1977-08-01 1978-11-28 Exxon Research & Engineering Company Hydroconversion with group IA, IIA metal compounds
DE3114766A1 (de) * 1980-04-15 1982-06-16 Rollan Dr. 89316 Eureka Nev. Swanson Verfahren zum umwandeln von kohle oder torf in gasfoermige kohlenwasserstoffe oder fluechtige destillate oder gemische hiervon
US4366045A (en) * 1980-01-22 1982-12-28 Rollan Swanson Process for conversion of coal to gaseous hydrocarbons
US4468316A (en) * 1983-03-03 1984-08-28 Chemroll Enterprises, Inc. Hydrogenation of asphaltenes and the like
US4545891A (en) * 1981-03-31 1985-10-08 Trw Inc. Extraction and upgrading of fossil fuels using fused caustic and acid solutions
US4606812A (en) * 1980-04-15 1986-08-19 Chemroll Enterprises, Inc. Hydrotreating of carbonaceous materials
US5059307A (en) * 1981-03-31 1991-10-22 Trw Inc. Process for upgrading coal
US5085764A (en) * 1981-03-31 1992-02-04 Trw Inc. Process for upgrading coal
US5250181A (en) * 1991-06-17 1993-10-05 Exxon Research And Engineering Company Process for removing elemental sulfur from fluids
US5695632A (en) * 1995-05-02 1997-12-09 Exxon Research And Engineering Company Continuous in-situ combination process for upgrading heavy oil
US5935421A (en) * 1995-05-02 1999-08-10 Exxon Research And Engineering Company Continuous in-situ combination process for upgrading heavy oil
US6210564B1 (en) 1996-06-04 2001-04-03 Exxon Research And Engineering Company Process for desulfurization of petroleum feeds utilizing sodium metal
US20050145545A1 (en) * 2003-04-17 2005-07-07 Trans Ionics Corporation Desulfurization of petroleum streams using metallic sodium
US20050161340A1 (en) * 2004-01-26 2005-07-28 Ceramatec, Inc. Process for the recovery of materials from a desulfurization reaction
US20060065577A1 (en) * 2004-09-30 2006-03-30 Dysard Jeffrey M Desulfurizing organosulfur heterocycles in feeds with supported sodium
US20080268327A1 (en) * 2006-10-13 2008-10-30 John Howard Gordon Advanced Metal-Air Battery Having a Ceramic Membrane Electrolyte Background of the Invention
US20090061288A1 (en) * 2007-09-05 2009-03-05 John Howard Gordon Lithium-sulfur battery with a substantially non-pourous membrane and enhanced cathode utilization
US20090134059A1 (en) * 2005-12-21 2009-05-28 Myers Ronald D Very Low Sulfur Heavy Crude oil and Porcess for the Production thereof
US20090134842A1 (en) * 2007-11-26 2009-05-28 Joshi Ashok V Nickel-Metal Hydride Battery Using Alkali Ion Conducting Separator
US20090159501A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Electrodesulfurization of heavy oils using a divided electrochemical cell
US20090159427A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Partial electro-hydrogenation of sulfur containing feedstreams followed by sulfur removal
US20090159503A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Electrochemical treatment of heavy oil streams followed by caustic extraction or thermal treatment
US20090159500A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Electrodesulfurization of heavy oils
US20090189567A1 (en) * 2008-01-30 2009-07-30 Joshi Ashok V Zinc Anode Battery Using Alkali Ion Conducting Separator
US20100046825A1 (en) * 2006-02-10 2010-02-25 Parallel Synthesis Technologies, Inc. Authentication and anticounterfeiting methods and devices
US20100089762A1 (en) * 2008-10-09 2010-04-15 John Howard Gordon Apparatus and Method For Reducing an Alkali Metal Electrochemically at a Temperature Below the Metal's Melting Temperature
US20100187124A1 (en) * 2008-08-05 2010-07-29 Koveal Russell J Process for regenerating alkali metal hydroxides by electrochemical means
US20100239893A1 (en) * 2007-09-05 2010-09-23 John Howard Gordon Sodium-sulfur battery with a substantially non-porous membrane and enhanced cathode utilization
US20110100874A1 (en) * 2009-11-02 2011-05-05 John Howard Gordon Upgrading of petroleum oil feedstocks using alkali metals and hydrocarbons
US8088270B2 (en) 2007-11-27 2012-01-03 Ceramatec, Inc. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides
US8216722B2 (en) 2007-11-27 2012-07-10 Ceramatec, Inc. Solid electrolyte for alkali-metal-ion batteries
US8323817B2 (en) 2008-09-12 2012-12-04 Ceramatec, Inc. Alkali metal seawater battery
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US8557101B2 (en) 2007-12-20 2013-10-15 Exxonmobil Research And Engineering Company Electrochemical treatment of heavy oil streams followed by caustic extraction
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US8771855B2 (en) 2010-08-11 2014-07-08 Ceramatec, Inc. Alkali metal aqueous battery
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US4123350A (en) * 1975-04-28 1978-10-31 Exxon Research & Engineering Co. Process for desulfurization of residua with sodamide-hydrogen and regeneration of sodamide
US4003824A (en) * 1975-04-28 1977-01-18 Exxon Research And Engineering Company Desulfurization and hydroconversion of residua with sodium hydride and hydrogen
US4007111A (en) * 1975-04-28 1977-02-08 Exxon Research And Engineering Company Residua desulfurization and hydroconversion with sodamide and hydrogen
US4076613A (en) * 1975-04-28 1978-02-28 Exxon Research & Engineering Co. Combined disulfurization and conversion with alkali metals
US3976559A (en) * 1975-04-28 1976-08-24 Exxon Research And Engineering Company Combined catalytic and alkali metal hydrodesulfurization and conversion process
US4127470A (en) * 1977-08-01 1978-11-28 Exxon Research & Engineering Company Hydroconversion with group IA, IIA metal compounds
US4119528A (en) * 1977-08-01 1978-10-10 Exxon Research & Engineering Co. Hydroconversion of residua with potassium sulfide
US4366045A (en) * 1980-01-22 1982-12-28 Rollan Swanson Process for conversion of coal to gaseous hydrocarbons
DE3114766A1 (de) * 1980-04-15 1982-06-16 Rollan Dr. 89316 Eureka Nev. Swanson Verfahren zum umwandeln von kohle oder torf in gasfoermige kohlenwasserstoffe oder fluechtige destillate oder gemische hiervon
US4606812A (en) * 1980-04-15 1986-08-19 Chemroll Enterprises, Inc. Hydrotreating of carbonaceous materials
US4545891A (en) * 1981-03-31 1985-10-08 Trw Inc. Extraction and upgrading of fossil fuels using fused caustic and acid solutions
US5059307A (en) * 1981-03-31 1991-10-22 Trw Inc. Process for upgrading coal
US5085764A (en) * 1981-03-31 1992-02-04 Trw Inc. Process for upgrading coal
US4468316A (en) * 1983-03-03 1984-08-28 Chemroll Enterprises, Inc. Hydrogenation of asphaltenes and the like
US5250181A (en) * 1991-06-17 1993-10-05 Exxon Research And Engineering Company Process for removing elemental sulfur from fluids
US5695632A (en) * 1995-05-02 1997-12-09 Exxon Research And Engineering Company Continuous in-situ combination process for upgrading heavy oil
US5935421A (en) * 1995-05-02 1999-08-10 Exxon Research And Engineering Company Continuous in-situ combination process for upgrading heavy oil
US6210564B1 (en) 1996-06-04 2001-04-03 Exxon Research And Engineering Company Process for desulfurization of petroleum feeds utilizing sodium metal
US7192516B2 (en) 2003-04-17 2007-03-20 Trans Ionics Corporation Desulfurization of petroleum streams using metallic sodium
US20050145545A1 (en) * 2003-04-17 2005-07-07 Trans Ionics Corporation Desulfurization of petroleum streams using metallic sodium
US20050161340A1 (en) * 2004-01-26 2005-07-28 Ceramatec, Inc. Process for the recovery of materials from a desulfurization reaction
US7897028B2 (en) 2004-01-26 2011-03-01 Ceramatec, Inc. Process for the recovery of materials from a desulfurization reaction
US20060065577A1 (en) * 2004-09-30 2006-03-30 Dysard Jeffrey M Desulfurizing organosulfur heterocycles in feeds with supported sodium
US7507327B2 (en) 2004-09-30 2009-03-24 Exxonmobil Research And Engineering Company Desulfurizing organosulfur heterocycles in feeds with supported sodium
US20090134059A1 (en) * 2005-12-21 2009-05-28 Myers Ronald D Very Low Sulfur Heavy Crude oil and Porcess for the Production thereof
US20100046825A1 (en) * 2006-02-10 2010-02-25 Parallel Synthesis Technologies, Inc. Authentication and anticounterfeiting methods and devices
US20080268327A1 (en) * 2006-10-13 2008-10-30 John Howard Gordon Advanced Metal-Air Battery Having a Ceramic Membrane Electrolyte Background of the Invention
US8012633B2 (en) 2006-10-13 2011-09-06 Ceramatec, Inc. Advanced metal-air battery having a ceramic membrane electrolyte
US20100239893A1 (en) * 2007-09-05 2010-09-23 John Howard Gordon Sodium-sulfur battery with a substantially non-porous membrane and enhanced cathode utilization
US8771879B2 (en) 2007-09-05 2014-07-08 Ceramatec, Inc. Lithium—sulfur battery with a substantially non-porous lisicon membrane and porous lisicon layer
US20090061288A1 (en) * 2007-09-05 2009-03-05 John Howard Gordon Lithium-sulfur battery with a substantially non-pourous membrane and enhanced cathode utilization
US20090134842A1 (en) * 2007-11-26 2009-05-28 Joshi Ashok V Nickel-Metal Hydride Battery Using Alkali Ion Conducting Separator
US9209445B2 (en) 2007-11-26 2015-12-08 Ceramatec, Inc. Nickel-metal hydride/hydrogen hybrid battery using alkali ion conducting separator
US8722221B2 (en) 2007-11-26 2014-05-13 Ceramatec, Inc. Method of discharging a nickel-metal hydride battery
US8159192B2 (en) 2007-11-26 2012-04-17 Ceramatec, Inc. Method for charging a nickel-metal hydride battery
US8012621B2 (en) 2007-11-26 2011-09-06 Ceramatec, Inc. Nickel-metal hydride battery using alkali ion conducting separator
US8216722B2 (en) 2007-11-27 2012-07-10 Ceramatec, Inc. Solid electrolyte for alkali-metal-ion batteries
US8088270B2 (en) 2007-11-27 2012-01-03 Ceramatec, Inc. Process for recovering alkali metals and sulfur from alkali metal sulfides and polysulfides
US7985332B2 (en) 2007-12-20 2011-07-26 Exxonmobil Research And Engineering Company Electrodesulfurization of heavy oils using a divided electrochemical cell
US20090159500A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Electrodesulfurization of heavy oils
US20090159503A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Electrochemical treatment of heavy oil streams followed by caustic extraction or thermal treatment
US20090159501A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Electrodesulfurization of heavy oils using a divided electrochemical cell
US8557101B2 (en) 2007-12-20 2013-10-15 Exxonmobil Research And Engineering Company Electrochemical treatment of heavy oil streams followed by caustic extraction
US8075762B2 (en) 2007-12-20 2011-12-13 Exxonmobil Reseach And Engineering Company Electrodesulfurization of heavy oils
WO2009082466A1 (en) * 2007-12-20 2009-07-02 Exxonmobil Research And Engineering Company Electrodesulfurization of heavy oils
US20090159427A1 (en) * 2007-12-20 2009-06-25 Greaney Mark A Partial electro-hydrogenation of sulfur containing feedstreams followed by sulfur removal
US8177963B2 (en) 2007-12-20 2012-05-15 Exxonmobil Research And Engineering Company Partial electro-hydrogenation of sulfur containing feedstreams followed by sulfur removal
WO2009082456A1 (en) * 2007-12-20 2009-07-02 Exxonmobil Research And Engineering Company Electrodesulfurization of heavy oils using a divided electrochemical cell
US20090189567A1 (en) * 2008-01-30 2009-07-30 Joshi Ashok V Zinc Anode Battery Using Alkali Ion Conducting Separator
US10320033B2 (en) 2008-01-30 2019-06-11 Enlighten Innovations Inc. Alkali metal ion battery using alkali metal conductive ceramic separator
US8486251B2 (en) 2008-08-05 2013-07-16 Exxonmobil Research And Engineering Company Process for regenerating alkali metal hydroxides by electrochemical means
US20100187124A1 (en) * 2008-08-05 2010-07-29 Koveal Russell J Process for regenerating alkali metal hydroxides by electrochemical means
US8323817B2 (en) 2008-09-12 2012-12-04 Ceramatec, Inc. Alkali metal seawater battery
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IT987858B (it) 1975-03-20
GB1431491A (en) 1976-04-07
DE2326236A1 (de) 1973-12-06
JPS5621782B2 (de) 1981-05-21
FR2185671A1 (de) 1974-01-04
CA1001978A (en) 1976-12-21
FR2185671B1 (de) 1978-09-29
NL7307131A (de) 1973-11-27
JPS4942702A (de) 1974-04-22

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