text:
|Publication number
|Publication type
|Application number
|Publication date
|Feb 7, 1978
|Filing date
|Jul 22, 1976
|Priority date
|Jul 22, 1976
|Publication number
|Clyde C. Hawkins, Jesse R. Hawkins
|Original Assignee
|Hawkins Enterprises, Inc.
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (7), Referenced by (45), Classifications (16)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates to fuel systems for the internal combustion engines of automobiles or similar vehicles. and more particularly relates to fuel systems of the type which attempt to achieve increased operating efficiency and/or reduced exhaust-pollution, from the engines serviced thereby, by heating of the fuel conducted to such engines.
Prior patents disclosing fuel systems of the aforesaid general type, which incorporate fuel heating means therein, include the following: U.S. Pat. Nos. 3,807,377, 3,780,714, 3,797,468, 3,472,214, 3,286,703, 2,974,656, 2,748,758 and 2,179,235.
If a fuel system of the type in question is to operate in a safe and satisfatory manner, the heated fuel (usually gasoline) delivered thereby to the engine serviced by the system must be maintained within a relatively limited temperature range. The optimum fuel temperature will vary in accordance with the characteristics of the engine, carburator and the like of the particular automobile or similar vehicle in association with which the fuel system is employed. Therefore, while a fuel system incorporating a non-adjustable fuel heater may perform satisfactorily in one particular vehicle, the performance of the same fuel system in another vehicle may be totally inadequate and even detrimental or dangerous. It is also important, even in connection with a fuel system adapted for use in only one particular vehicle, that the heat output of the fuel heater be automatically regulated and varied in such a manner as to maintain the heated fuel at its optimum temperature irrespective of changes in the operating conditions of the vehicle. In the absence of adequate automatic regulation of the heat output of the fuel heater, a fuel system which performs satisfactorily when the vehicle is cruising will likely severely overheat the fuel when such vehicle is coasting or is stationary. Conversely, a system which performs satisfactorily when the vehicle is coasting or stationary will inadequately heat the fuel delivered to the carburator when the vehicle is cruising unless at such time the heat output of the fuel heater is increased to accommodate the increased fuel flow. The same problem, -- i.e., that of the fuel entering the carburator being at a temperature less than the desired optimum one -- will also arise if the fuel is heated to only its ultimate optimum temperature at the heater and is then allowed to undergo significant cooling during its thereafter ensuing passage from the heater to the carburator. Detection and regulation of the temperature of the fuel are for the most part meaningless functions unless the desired end-result, which is maintenance of an optimum fuel-temperature at a location closely adjacent the carburator of the system, is realized thereby.
Another major problem that has heretofore been encountered is that of "vapor lock" of the fuel pump components of fuel systems incorporating fuel heaters. Such problem is a serious one since as long as a "vapor lock" condition persists, the vehicle is virtually useless. Whatever benefits it might otherwise possess or yield, therefore, a fuel system which is subject to "vapor lock" of its fuel pump is not satisfactory and will not enjoy public acceptance.
A fuel system of the type in question should also be economical to manufacture, install and maintain. From the installation viewpoint, it is highly desirable that the system be readily installable within not only new vehicles, but also within existing vehicles of the many different makes and models presently in use. This requires that the system be capable of utilizing, with little and preferably no modifications thereto, the existing carburator, fuel pump and other major fuel-handling components of the vehicle at hand. It also requires that the fuel heater component of the system be of a sufficiently compact size and versatile design as to be mountable and usable in whatever location and limited space as might be available in the engine comparts of different vehicles.
Lastly, a system of the type in question should for reasons of safety be of a durable "closed" construction not susceptible to fuel leakage and not requiring the accumulation of large quantities of fuel within any components located inside of the engine compartment of a vehicle.
The present invention provides an improved fuel system of the hereinbefore noted type which possesses the desirable attributes and is free from the deficiencies discussed above. The improved system may be installed with facility in virtually any vehicle, utilizing the existing carburator and fuel pump present in such vehicle, and includes fuel heating means interposed between the fuel pump and the carburator for heating fuel conducted therethrough during its passage from the pump to the carburator. Adjustable control means automatically regulates the operation of the fuel heating means in accordance with the temperature of the fuel passing downstream therefrom to the carburator. To minimize heat-transfer to and possible "vapor-lock" of the fuel pump, cooling means are provided within that part of the system intermediate the fuel heater and the fuel pump. The system is durable, safe and inexpensive, and is highly effective in significantly increasing the efficiency and reducing the exhaust pollution of a vehicle engine.
Still other features and benefits of the invention will be apparent from the following description of an illustrative embodiment thereof, which should be read in conjunction with the accompanying drawing, in which:
FIG. 1 is a schematic view of a fuel system in accordance with the invention, in association with the internal combustion engine and other components of an automobile or similar vehicle; and
FIG. 2 is an enlarged elevational view, partially broken away to better disclose details of construction, of the fuel heater and immediately adjacent components of the system of FIG. 1.
Referring first to FIG. 1 of the drawing, the numeral 10 designates the internal combustion engine of an automobile or similar vehicle (not shown), which engine is serviced by a fuel system 12 and a cooling system 14. In addition to other components hereinafter described, fuel system 12 includes a fuel reservoir or tank 16, a fuel pump 18 and a carburator 20. Tank 16, pump 18 and carburator 20 may be and illustratively are of conventional construction, and in the present system 12 perform their standard functions of supplying desired quantities of fuel, usually gasoline, to engine 10 during operation thereof. Engine-cooling system 14 also may be and illustratively is comprised of standard and well-known components, including a water pump 22, fan 24 and radiator 26 disposed forwardly of engine 10 and suitably connected thereto such that during operation of the engine, cool water (which may of course be in solution with anti-freeze or other additives) is circulated from radiator 26 to and through the water jacket (not shown) of engine 10, as a consequence of which the water becomes heated, and then is circulated back to and through radiator 26 for cooling by air currents passed forwardly to rearwardly (from right to left as viewed in FIG. 1) through such radiator. The aforesaid air currents are of course generated at all times during operation of engine 10 by the fan 24 driven thereby, and are supplemented by those resulting from motion of the vehicle (not shown) driven by engine 10 when such vehicle is moving in a forward direction.
In accordance with the present invention, fuel system 12 further includes fuel heating means 28 interposed intermediate fuel pump 18 and carburator 20 for heating the fuel during its passage from pump 18 to carburator 20; control means, including an adjustable and automatic valve member 30, and an associated temperature-detecting element 62, for regulating the operation of fuel heater 28 in accordance with the temperature of the fuel passing downstream from it to carburator 20; and cooling means 32 disposed within that part of system 12 intermediate fuel heater 28 and fuel pump 18 for minimizing heat-transfer in an "upstream" direction through the system from heater 28 to pump 18.
Referring now also to FIG. 2, fuel heater 28 comprises a generally cylindrical casing 34 to the opposite ends of which are welded or otherwise permanently secured identical end members 36,36' having central tubular projections 38,38' respectively formed integrally therewith and projecting axially outwardly therefrom. The foregoing components are preferably formed of brass or similar material which is rigid and durable, and which constitutes a relatively good conductor of heat. A pair of identical mounting blocks 40,40', which preferably are also formed of metallic material, are respectively disposed adjacent projections 38,38' of end members 36,36'. Mounting block 40 has a central bore 42 extending through and between opposed faces thereof, which bore communicates intermediate its length with a second bore 44 extending inwardly through another face of block 40. Projection 38 of end member 36 is received within one end of central bore 42 of mounting block 40, and is welded or otherwise suitably secured thereto. Adjacent the opposite end of central bore 42 of block 40, suitable fittings 46 connect a conduit 48, leading from fuel pump 18, to a conduit 50 which extends axially through bore 42 and projection 38 and which within casing 34 is provided with a plurality of helical coils which are concentric with the axis of the casing and are in spaced adjacent relationship to its cylindrical inner surface. Conduit 50 is formed of heat-conductive and corrosion-resistant metallic material, such as copper tubing, and conduit 48 normally would be formed of the same type of material. The second bore 44 within mounting block 40 is connected, as by a fitting 52 and a rubber hose or other suitable conduit 54, to the "suction" or low-pressure side of the engine-cooling water-circulating system 14 associated with engine 10. The place of connection of conduit 54 to system 14 is adjacent a location where water pump 22 produces a maximum suction force.
The mounting block 40' adjacent the opposite end of heater 28 is provided with bores and fittings identical to those described in connection with mounting block 40, and is connected to projection 38' of end member 36' in the same manner as projection 38 is connected to mounting block 40. The "outlet" or left-most end portion of conduit 50 projects axially and freely through projection 38' and the central bore (not shown) of mounting block 40', and communicates with a copper-tubing conduit 56 extending to carburator 20. The second bore (not shown) of block 40' is connected as by a rubber hose or similar conduit 58, within which valve member 30 is interposed, to engine-cooling water-circulating system 14 at a location therein effective to cause hot water from such system to pass into and through block 40' when valve member 30 is in an open condition.
Valve 30 is of a commercially-available type effective to automatically vary the flow of hot water through conduit 58 in response to variations in temperature, outside of a desired range manually selectable by rotation of an adjustment screw 60 associated with the valve, sensed by a temperature-detecting bulb 62 connected to valve 30 by a capillary tube 64. Bulb 62 is disposed in engagement with the heat-conductive conduit 56 interconnecting fuel heater 28 and carburator 20, at a location along the length of such conduit closely adjacent carburator 20. A sheath of insulating material 66 encircles the entire length of conduit 56 and encloses, in addition to the conduit itself, bulb 62 and as much as possible of the capillary tube 64 interconnecting such bulb and valve 30. The primary function of the sheath of insulating material 66 is to so shield bulb 62 from air currents, radiated engine heat and the like as to insure that the temperature sensed by bulb 62 is that of the heated fuel passing through that part of conduit 56 closely adjacent carburator 20. A secondary function of the sheath of insulating material 66 is to minimize heat-loss from the fuel passing from heater 28 to carburator 20.
The cooling means 32 associated with the conduit 48 interconnecting fuel pump 18 and heater 28 illustratively comprises a sinuously-curved portion of such conduit which is disposed forwardly of radiator 26 in exposed relationship to the previously-mentioned air currents directed toward such radiator during operation of engine 10. At least the aforesaid sinuously-curved portion of conduit 50 is formed of copper tubing or similar metallic material constituting a good conductor and radiator of heat. To increase its heat-dissipating capacity, cooling means 32 may and illustratively does further include a plurality of heat-radiating fin elements 68 which are welded or otherwise suitably secured in encircling relationship to the aforesaid sinuously-curved portion of conduit 48. Although otherwise shown in FIG. 1 for convenience of illustration, the various parallel sections of the sinuously-curved portion of conduit 48 would of course normally not extend in their length direction in a common horizontal plane.
During operation of engine 10 hot water from engine-cooling system 14 is circulated through conduit 58 to mounting block 40', thence axially through heater 28 (from left to right as viewed in the drawing) to mounting block 40, and thence through conduit 54 back to system 14. At the same time gasoline or similar liquid fuel from fuel tank 16 passes through conduit 70 to fuel pump 18; thence through conduit 48 to mounting block 40; thence through the conduit 50 extending through block 40, heater 28 and block 40'; and finally through conduit 56 to carburator 20. In passing through heater 28 the fuel is heated to an extent dependent upon the then-existing magnitude of the counter-flow of hot water introduced into the heater through hose 58. The magnitude of such flow, and therefore the operation of heater 28, is regulated by valve 30 in accordance with the setting of adjustment screw 60 and the temperature of the fuel entering carburator 20, as detected by the bulb 62 disposed in engagement with that portion of conduit 56 closely adjacent the carburator. The optimum fuel temperature at the aforesaid location will usually be within the range of approximately 125�-135� F, but will vary depending upon the individual characteristics of the particular engine 10 serviced by fuel system 12. However, in any particular installation of fuel system 12 the optimum fuel temperature and setting of adjustment screw 60 can be readily determined by empirical means: i.e., by comparison of the increased efficiency of engine 10, as reflected by the miles-per-gallon fuel consumption of the vehicle driven by such engine, at different settings of adjustment screw 60. Once the optimum fuel temperature and setting of adjustment screw 60 are determined for a particular vehicle, further adjustments of screw 60 are not required and the operation of heater 28 is thereafter automatically and continuously regulated by valve 30 in response to the detection by bulb 62 of variations from the optimum temperature of the fuel passing to carburator 20. If the detected fuel temperature is too low, valve 30 opens to increase the flow of hot water through conduit 58 and heater 28. Conversely, if the detected temperature is too high, valve 30 closes to decrease, or to entirely stop, the flow of hot water through conduit 58 and heater 28. When a complete closure of valve 30 occurs, most if not all of the residual water within heater 28 is rapidly evacuated therefrom through conduit 54 and the heater rapidly cools, particularly when its major components are formed of uninsulated heat-conductive material, to ambient temperature. System 12 therefore does not permit an overheated fuel condition to exist long enough for any detrimental or dangerous consequences to ensue therefrom.
The provisions of cooling means 32 within conduit 48 obviates the possibility of such conduit and/or the fuel therewithin transferring such heat in an "upstream" direction to fuel pump 18 as to cause "vapor-lock" of the fuel pump. It should be noted that this highly desirable result is achieved without sacrificing the safety-benefits inherent in the use throughout system 12 of fuel conduits formed entirely of copper tubing or the like, as opposed to conduits formed of other materials.
Although heater 28 is shown in the drawing in a substantially horizontal orientation, its operation is equally satisfactory if not even superior when mounted, as by means of suitable fasteners (not shown) connected to blocks 40,40', in a vertical orientation. Additionally, heater 28 is of a compact size and need not be mounted at any particular location within the engine-compartment of a vehicle. For the foregoing reasons, in conjunction with the fact that fuel heater 28 can be used in association with a standard carburator and fuel pump, it will be appreciated that the present fuel system 12 can be readily installed in virtually any vehicle. It will also be apparent that then the fuel system will require little if any maintenance and will be exceedingly reliable and safe, as well as effective, in its operation.
While a preferred embodiment of the invention has been specifically shown and described, this was for purposes of illustration only, and not for purposes of limitation, the scope of the invention being in accordance with the following claims.
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|International Classification
|Cooperative Classification
|European Classification


text:
|Publication number
|Publication type
|Application number
|PCT number
|Publication date
|Feb 27, 2001
|Filing date
|Jan 10, 1997
|Priority date
|Jan 10, 1996
|Fee status
|Also published as
|Publication number
|Jainagesh A. Sekhar, Vittorio De Nora, Jean-Jacques Duruz
|Original Assignee
|Moltech Invent S.A
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (7), Non-Patent Citations (1), Classifications (28), Legal Events (8)
|External Links: USPTO, USPTO Assignment, Espacenet
This invention relates in general to the treatment of carbon bodies which are exposed to high temperature oxidizing gases, in order to improve the resistance of the bodies to deterioration by these oxidizing gases.
The invention is concerned in particular with carbon bodies which are used as components of electrolytic cells for the production of aluminum, for example by the electrolysis of alumina in a molten fluoride electrolyte such as cryolite, wherein in use of the cell the carbon components are exposed to air and anodically-generated oxidizing gases.
One aspect of the invention is the method of treating such cell components or other carbon bodies to improve their resistance to deterioration by oxidizing gases at high temperatures. Further aspects of the invention concern the treated cell components and other carbon bodies, aluminum production cells including these components, an improved, preferably less odoriferous treating liquid, preferably with a reduced susceptibility to foaming, and use of this treating liquid to improve the oxidation resistance of carbon bodies.
Aluminum is produced conventionally by the Hall-Héroult process, by the electrolysis of alumina dissolved in cryolite-based molten electrolytes at temperatures up to around 950° C. In Hall-Héroult cells, the anodes are usually pre-baked carbon blocks that are consumed by the electrochemical reaction, corroded by contact with the electrolyte and disintegrated by the air and/or oxidizing gases present. Söderberg anodes made of a coherent carbon mass which solidifies in situ are also used.
Pre-baked anodes for aluminum production are made of a matrix of petroleum coke with pitch as binder. Their production involves various phases including preparing and treating the starting materials, mixing, forming and calcining at high temperature, followed by securing the current supply member by rodding.
The resistance of that part of the anode which remains outside the bath during cell operation is of paramount importance, not only to decrease the amount of anode consumption above the theoretical requirement but also to reduce the formation of carbon dust which is a cause of a reduction in current efficiency and an increase in cell temperature, and which must be eliminated when it collects on bath surface.
Of the several attempts to protect the anode, none has so far been satisfactory. The normal protection by aluminum spraying is costly and not always impervious. The oxidation of the carbon anodes, in the Hall-Héroult cell, outside the bath leads to a loss for the aluminum producer. Typically, instead of the theoretical consumption of 0.33 kg of carbon per ton of aluminium, often more than 0.43 kg is lost, the difference being caused mainly by air and CO2 burn.
Many elements or compounds catalyze the oxidation reaction of carbons but the inhibition of the same reaction is more difficult to achieve. In general, the oxidation reactivity of carbon is reduced with absorbers, or with ceramic protection layers. Several absorber additives have been reported, such as metal, halogen compounds, and incorporated nitrogen. Ceramic protecting layers have been proposed, formed by low melting liquid glass, such as B2O3, Cr2O3, silica, etc.
The oxidation prevention treatment processes contemplated for the anode can be divided into two different groups, one is an additive added after the anode baking, the other is an additive added into the carbon paste. To date, only an aluminium coating protection treatment, or a thick layer of alumina and cryolite, has worked reasonably well for oxidation protection of commercial pre-baked anodes, but has several drawbacks, such as cost and difficulties in the cell operation. No oxidation protection has so far been suggested for Söderberg continuous anodes. Several other oxidation prevention treatments have worked well in the laboratory but have fallen short of the expected performance when the same treatments have been applied to the anodes tested in commercial cells. No apparent reason has been forthcoming and the discussion of such an effect has invariably been directed towards the possibility of the composition of the anode gases being the reason for such a difference.
When boron has been added to the anode paste in the form of elemental boron or boron compound, the oxidation rate of the carbon has been reduced but the contamination of aluminum is unacceptable.
Recently, U.S. Pat. No. 5,486,278 (Mangienello et al.) has disclosed a treatment process which has been shown to significantly reduce the oxidation of the anode in the laboratory as well in commercial cell tests in the pre-baked carbon anodes. This method comprises treating the anode or other component in a boron-containing liquid to intake the boron-containing liquid to a selected depth over parts of the surface to be protected, this selected depth being in the range 1-10 cm, preferably at least 1.5 cm and at most about 5 cm, preferably still at least about 2 cm and at most about 4 cm. This method was found to significantly reduce the oxidation of pre-baked anodes in laboratory tests and in commercial test cells. However, as discussed in detail below, it has been found unexpectedly that the greatly improved oxidation resistance obtained with this treatment is partly offset by a strength loss which could lead to burn-off after a critical weight loss when the anode is subjected to stress. This could lead to problems when the components are scaled up to industrial size.
Problems like those described above for pre-baked carbon anodes apply also to the carbon cell sidewalls including a lower part submerged in the electrolyte and an upper part which is exposed to CO2-enriched air, and which disintegrate and wear away as a result of attack by oxidizing gases.
An object of the invention is to improve the resistance to oxidation of carbon bodies in particular carbon anodes or cell sidewalls of aluminum production cells by the incorporation of boron without the inherent drawbacks of the known proposals.
The invention is based on the insight that boron impregnated anodes and other carbon cell components made usually from petroleum coke and pitch suffer the drawback that the oxidation occurs particularly at the pitch location (bonding phase). With increasing time, the excess weight loss and disintegration of pitch (which is the bonding phase) reduces the overall mechanical strength so that after a certain time and above a certain temperature, when the weight loss reaches a critical amount (which may typically be about 8-10 wt %) the material reaches it brittleness limit and starts to collapse. In large components, this brittleness limit may be encountered in the cell before the main part of the anode has been consumed, and could lead to massive failure.
The invention provides a composition for the boron-containing impregnating liquid that minimizes attack in the pitch phase and hence improves the strength of the carbon while improving the oxidation resistance or at least maintaining it at the same level. The invention therefore aims to reduce the anode consumption by reducing anode brittleness and further improving the oxidation resistance. Similar advantages can be obtained with cell sidewalls or other carbon bodies such as Söderberg anodes, subjected to attack by oxidizing gases at high temperatures. A further improvement may be provided by making the impregnating liquid less odoriferous and/or less susceptible to foaming.
The invention provides a method of treating a carbon body, in particular a carbon-based anode or sidewall of an electrolytic cell for the production of aluminum in particular by the electrolysis of alumina in a molten flouride electrolyte such as cryolite, to improve the resistance thereof to deterioration by the attack of oxidizing gases, using boron in acceptable amounts in the surface parts exposed in use to oxidizing gases, in combination with selected agents and additives.
According to the invention, the boron-containing liquid contains at least one additive from the group consisting of aluminum compounds, calcium compounds, sodium compounds, magnesium compounds, silicon compounds, elemental carbon and elemental aluminum, said additive being in the form of a powder, in suspension, as a colloid, or in solution. The aluminum compounds and calcium compounds may be aluminum acetate boric, colloidal alumina, calcium acetate, calcium carbonate, calcium oxide and calcium aluminate. The silicon compound may be colloidal silica, which could advantageously react with the boron compound to form a boro-silicate glassy coating. Preferably a surfactant may be used as part of the treating liquid, in which case, advantageously, an anti-foaming agent is also included.
The anode impregnation treatment according to the invention provides a protected layer of one or more centimeters, in which the addition of the stated additive/s serves to minimize attack to the pitch binder phase and therefore improves the strength of the carbon when it is subjected to wear during use in the cell. The impregnation treatment also improves the oxidation resistance of the anode compared to impregnation with the boron compound alone, or at least maintains it at the same level.
The addition of aluminum compounds such as aluminum acetate boric and colloidal alumina decreases the oxidation rate and increases strength. The addition of calcium compounds acts as a strength reinforcing agent and also produces an improvement in oxidation rate.
Preferably, the treating liquid contains at least one aluminium compound and at least one calcium compound, which together form calcium aluminate which acts as a cement to reinforce the carbon body.
The treatment method applies particularly to pre-baked carbon anodes, which are subject to mechanical stress during operation. With the treatment, damage to the outer surface is not detrimental to the protection against oxidation, due to the thickness of the treatment which provides a long-lasting protective effect as the inside part of the anode wears away slowly during use, with greatly improved mechanical resistance of the carbon.
The treatment method can also be applied to the outer part of Söderberg anodes as they move down in the conventional manner.
The treatment method is also applicable to a cell sidewall, particularly the upper part of the cell sidewall that is exposed to air and the effect of oxidizing gases during use, as well as the lower part which is exposed to carbo-oxidation reactions with CO2 at the surface or to the part of the sidewall submerged in the electrolyte.
In the case of carbon bodies, in particular cell sidewalls, the protective effect can be enhanced by topcoating the exposed part of the impregnated sidewalls with a layer of refractory material, e.g. particulate diboride in a colloidal carrier, such as titanium diboride in colloidal alumina or colloidal silica, as described in WO 93/25731.
The following details of the treatment process are given with reference to the particular components and method used, but also apply in general to any carbon component subjected to attack by oxidizing gases.
The treating liquid comprises a boron compound such as B2O3, boric acid or tetraboric acid dissolved in a solvent, further including at least one additive as described above, and preferably containing at least one surface-active agent. Good results have been achieved with boric acid and precursors of boric acid that form B2O3. Borates have not been found to give as good results.
The treating liquid preferably contains 5-60 weight % of the boron compound or mixture of a plurality of boron compounds, preferably in an aqueous solvent as a temperature in the range from 10° to 200° C., preferably 20° C. to 120° C. and more preferably 60° C. to 90° C., these conditions ensuring excellent penetration of the treating liquid into the porous carbon. The additive is preferably added in a weight quantity up to two times the weight quantity of boron compound (or mixture of boron compounds), more preferably in a weight quantity not exceeding the amount of boron compound (or mixture of boron compounds), even more preferably the weight quantity of additive does not exceed about ⅓, most preferably no more than about ⅕, of the boron compound (or mixture of boron compounds). For treating liquids with 50-60 weight % of boron compounds, solvents like methanol, ethylene glycol or glycerin are used at a temperature of about 80° C. or above.
It is advantageous to carry out the treatment with a heated liquid in order to increase the solubility of the boron compound and decrease the treatment time, if necessary with preheating of the anode. When using an aqueous solvent based treating liquid, the liquid may advantageously be steamed on to the substrate without heating the substrate. Carrying the treatment out at ambient temperature is possible and also convenient because no special heating equipment is required. The temperature of the carbon body in preferably from 20° C. to 200° C.
At low temperatures, certain solvents such as methanol, ethylene glycol and glycerin will be preferred, possibly with additives to enhance the solubility of the boron compound, and the treatment time may be extended. When water is used as the solvent, surfactant agents, in particular tensio-active cationic agents devoid of components that would undesirably contaminate the aluminium produced and devoid of components that promote oxidation of the carbon, may be used. Anionic tensio-active agents can also be used. These surface-active agents may possibly be present together with other solubility improving agents such as tartaric acid or citric acid. The liquid may of course also be heated to improve and speed up the impregnation of the anode.
The use of surface active agents is an important factor to accelerate penetration of the liquid and to obtain impregnation to a sufficient depth of several centimeters in only a few minutes, since long treatment times could make the process impractical and uneconomical. The coefficient of diffusion of the liquid into the porous carbon structure and the wettability of the carbon by the liquid will influence the rate and the degree of penetration. Liquids with low surface tension providing an angle of contact with the carbon of less than 90° provide adequate wettability and facilitate penetration. A suitable high temperature will also enhance diffusion of the liquid.
When water is chosen as solvent, a surfactant such as those available under the trade names NONIDET P 40 and SPAN 85, from Fluka, and GLUCOPON 225, DEHYPON LS, QUAFIN LDM and QUAFIN CT, from Henkel, can be used in order to achieve an acceptable low treatment time. Preferably, the surfactant is used at a level ranging from 0.05 to 0.25 weight percent of the total treating liquid.
It has been observed that the use of a surfactant can cause foaming of the treating liquid, if the liquid is stirred for dispersion of the ingredients. If the surfactant is added after the addition of, and separate from, the other components, depending on the particular surfactant used, an unpleasant odor may also be encountered. No odor is encountered without foaming, although an odor is not always encountered when foaming is. For example, if the surfactant is added with the rest of the ingredients, foaming is observed, but no odor is observed. When the surfactant QUAFIN CT is used, foaming is observed as described above. If, however, an anti-foaming agent such as Dow Corning Antifoam 2210 is added separate from all other ingredients and immediately prior to addition of the surfactant, no foaming is observed. If the anti-foaming agent is added immediately after the surfactant, again no foaming or odor is observed.
A boron compound or mixtures of boron compounds is added to the solvent in a quantity sufficient to guarantee saturation or near saturation of the liquid upon heating, even leaving a deposit of the undissolved compound in the bottom of the vessel. The additive/s is/are also added in amounts compatible with their solubilities, generally in a quantity which does not exceed ⅓ (usually no more than about ⅕th) the amount of the boron compound/s.
A carbon body, in particular an anode or a side-wall to be treated is then immersed in the treating liquid. Immersion is continued for a set time, e.g. from 2-60 minutes, or until a desired intake of the solution into the treated surfaces.
Usually, a single impregnation suffices, but the impregnation and drying may be repeated, if necessary, until the treated anode surface is saturated with the treating liquid.
The vapors produced in the described conditions are not toxic and can be freely released into the air without a need for costly treatment installations.
The treatment time depends principally on the exposed surface area of the anode or other component and its porosity, as well as temperature. It has been observed that prolonging the treatment does not significantly increase boron concentration.
Anodes or other components are conveniently impregnated simply by dipping them into the treating liquid, which can take place in ambient conditions, but the impregnation may be assisted by the application of a pressure differential, by applying pressure or a vacuum. Other ways of speeding up impregnation can also be used, such as the application of ultrasounds. Alternative application methods include steaming, painting, dabbing, vacuum impregnation, coating and the like.
In the manner described above, the treating liquid impregnates the carbon anode/substrate to a depth of 0.5-10 cm, for example approximately 2 to 4 or 5 cm, with a concentration of boron in the impregnated surface of the carbon anode/substrate in the range from 100 ppm to 0.35%, or possibly even higher. Even with the highest achievable levels of boron concentration, the problem of process contamination is avoided because the protective boron compounds are present only in the surfaces needing protection, and only to a depth of a few centimeters or less. For a pre-baked anode, only the top surface and the top part of the side surfaces (shoulders) need to be impregnated.
By impregnating the parts of the anode to be protected—namely the side and top surfaces—with a small quantity of the boron treating liquid to a depth of 0.5 or several centimeters, and by the action of the aluminum and/or calcium compounds as additives to maintain the strength and improve the oxidation resistance, a long-lasting protective effect is achieved because the surfaces exposed to oxygen wear away very slowly over a long period, enhancing the strength while avoiding undesirable contamination of the aluminum produced.
The anode is usually made of petroleum coke and pitch, the anode having an open porosity of at least 5%, usually in the range 5 to 30%, preferably from 5 to 20%. The treatment can also be applied to porous carbon-based materials. For example, the anode may also be made of a composite carbon-based material comprising at least one further component such as refractory oxycompounds, in particular alumina. Examples of such materials are described in WO 93/25494. The composite material preferably comprises predominantly petroleum coke and pitch.
The impregnation treatment of a pre-baked anode according to the invention is made after calcining which provides the anode surface with the highest porosity, thereby improving the penetration of the liquid to a depth of 0.5 or several centimeters.
Oxidation of the anodes increases with porosity. Thus, with the impregnation treatment, the most porous part of the anode which is most prone to damage by oxidation, is protected. In other words, more porous parts of the surface to be protected are penetrated more and deeper by the composite boron-containing liquid, providing greater protection where needed.
The intake of the treating liquid into the anode/substrate can be monitored by checking the level of the treating liquid, or simply by the time of immersion for a given treating liquid and an anode/substrate of given porosity.
The top surfaces and at least the upper parts of the shoulders of a pre-baked anode can be immersed in the composite boron-containing liquid by dipping the anode upside down in the liquid. There is no need to treat the bottom of the anode where the electrochemical reaction takes place. In this way, only those parts of the anode which need protection are treated, and the amount of boron in the anode (and hence in the aluminum produced) is minimized.
When it is desired to treat rodded anodes, i.e. when the anode's current lead-in rod has already been connected to the top surface, it is more convenient to immerse the anodes with the rodded top side up. In this case, the lower surface of the anode which does not need protection against oxidation can for example either be temporarily blocked by a product or be temporarily isolated by a suitable device which prevents impregnation of the treating liquid and which product/device can be removed afterwards or which volatilizes.
As an alternative, the carbon substrates can be treated by spraying the treating liquid as steam under high pressure. In the case of Söderberg anodes, the treating liquid can be sprayed as steam onto the outer surface of the mass.
Tests have been conducted with carbon samples impregnated according to the invention, with non-impregnated carbon samples and with carbon samples impregnated with a boron-containing liquid alone, i.e. without the additives according to the present invention ("boron only samples").
The non-impregnated samples showed severe weight loss when subjected to oxidizing conditions above 500° C. The boron-only samples showed a greatly increased resistance to oxidation, i.e. a much lower weight loss when subjected to the same oxidizing conditions. However, surprisingly, the boron-only samples were found to suffer a strength loss such that when the weight loss reaches a critical amount (found in the test typically to be about 10%), the sample reaches its brittleness limit and is liable to collapse when subjected to stress.
Carbon samples impregnated according to the invention showed improved strength compared to the "boron only " samples under the same oxidizing conditions, with an equivalent or improved oxidation resistance.
The mechanism involved was investigated based on the fact that the carbon consists at least of two major phases, namely the petroleum coke particles and the pitch binder. The petroleum coke carbon and coked pitch carbon (calcined) were treated separately with the boron-only liquid to examine the influence of the treatment on the individual components when subjected to oxidation tests. Visual results indicated that a glassy layer was formed on the surface of the petroleum coke carbon. The petroleum carbon coke particles were not disintegrated after oxidation. However, disintegration was observed for the coked pitch carbon under similar conditions.
The results indicate that the oxidation rate of the pitch carbon is higher than that of the petroleum coke carbon. This high oxidation rate is on account of the amorphous phase and large surface area of the pitch carbon. The oxidation rate difference between two types of carbon is enhanced when the pre-baked carbon anodes are treated with an oxidation prevention treatment. The preferential oxidation of pitch carbon makes the bonding phase (binder) fail early and can lead to damage because of a loss in strength. The strength loss by the preferential oxidation is indicated by a diametral tensile strength test. When a boron-only treatment is used, the preferential oxidation is enhanced and may lead to fracture of an anode even before significant oxidation. However, when a treatment with the additives according to the present invention is used, the preferential oxidation is suppressed and strength loss is limited.
For pre-baked anodes used in full-scale cells, it has been found that a brittleness limit may be encountered prior to oxidation damage. This brittleness limit is encountered in anodes which are impregnated with oxidation prevention liquids which increase the oxidation rate difference between the several phases present in the anode. Therefore several treatments which worked well in the laboratory are subject to failure when applied to commercial anodes. The treatment according to the present invention has been shown to significantly reduce the oxidation of the anode in laboratory tests as well as in commercial cell tests. Additionally, this treatment suppresses the onset of the brittleness problem. The invention thus provides an anode treatment process which can be successfully applied to commercial anodes.
The carbon consumption due to air-oxidation of anodes treated according to the present invention corresponds to about 10-15% of the maximum consumption, which is comparable to what can be achieved with traditional aluminum protective coatings. Thus, the present invention provides an excellent and long-lasting protective effect at much less cost and with less risk of imperfections in the protection than with traditional aluminium protective coatings, and with better strength and oxidation resistance compared to impregnation with boron only treating liquids.
The components of the treating liquid are inexpensive and are non-polluting both for the aluminum production process and for the environment. The methods of the present invention are simple to carry out, and the treated surfaces are uniformly impregnated with the boron compounds, leading to reliability in use because of uniform wear to the exposed surfaces of the anode or sidewall. Also, as boron acts as a "negative catalyst," it is possible to make the anode and sidewall from carbon containing a higher content of vanadium, thereby reducing the cost of raw materials. Incorporation of the additives according to the present invention minimizes strength loss so that large scale anodes or sidewalls or other components can be made with improved oxidation resistance.
In addition to the above-described methods, the invention also concerns a carbon body which has a part of its surface exposed during use to high temperature oxidizing gases, said surface part being treated, to improve the resistance thereof to deterioration by said oxidizing gases, by impregnation with a boron-containing treating liquid which further contains at least one additive from the group consisting of aluminum compounds, calcium compounds, sodium compounds, magnesium compounds, silicon compounds, elemental carbon, elemental aluminium, said additive being in the form of powder, in suspension, as a colloid, or in solution.
Such a body may be a cell component of an aluminum production cell treated by the method set out above.
The impregnation treatment can also be applied to a carbon mass forming a self-feeding Söderberg anode, preferably by treating only the part of the mass subjected to oxidation by air and anodically-evolved oxidizing gases. The invention also concerns an electrolytic cell for the production of aluminium, in particular by the electrolysis of alumina in a molten fluoride electrolyte such as cryolite, comprising a pre-baked or Söderberg anode, or a sidewall or other component, as set out above, the anode or sidewall or other component being installed with the treated surfaces in contact with air and oxidizing gases released during operation of the cell.
The invention also concerns the treating liquid itself which, in a preferred formulation, contains, per 100 ml of water (including a small quantity of a surface-active agent), 2-10 grams of boron (as metal in the form of a boron compound) and as additives, aluminum acetate boric together with at least one of calcium acetate and calcium carbonate in a total amount of additives not exceeding the amount of boron. Another preferred formulation of the treating liquid contains, per 100 ml of water (including a small quantity of a surface-active agent), 2-6 grams of boron (in the form of a boron compound) and, as additives, aluminum and/or calcium compounds in a weight quantity of up to two time the weight quantity of the boron. Yet another preferred formulation of the treating liquid contains, per 100 ml of water (including a small quantity of a surface-active agent), 20-30 grams of boron (in the form of a boron compound) and, as additives, at least one compound selected from the group consisting of aluminum compound and calcium compounds in a total weight quantity not exceeding two time the weight quantity of the boron.
Another aspect of the invention is use of the treating liquid to improve the resistance of a carbon body to deterioration by the attack of oxidizing gases at high temperatures.
A further inventive feature is that at the end of the service life of the boron-impregnated anodes, the remaining anode butt can be treated by thermal means or by means of water or another solvent or solvents, or by spray washing, to remove the remaining boron compounds, before recycling the remaining carbon to be mixed with fresh carbon for the manufacture of new anodes. By processing the used anode butts in this way, the residual boron is removed from the carbon, so that the new anodes including the recycled carbon do not unwantedly contain boron throughout their mass which would increase the boron level in the product aluminium.
The invention will be further described by the way of example, and compared to the prior art, with reference to the accompanying drawings wherein:
FIG. 1 is a graph of strength vs. weight loss for untreated samples and comparative samples impregnated with boron only;
FIG. 2 is a similar graph on which are also plotted the results for samples impregnated with boron and alumina and/or calcium compounds according to the invention; and
FIG. 3 is a comparative graph showing oxidation rates of steam treated, dip-treated and untreated anodes at 600° C.
Carbon anode samples were cut from pieces of commercial pre-baked anodes of a Hall-Héroult cell. The samples were fully dried at 100-250° C. for a drying time depending on their size. For example, for samples consisting of a 3 cm long cylinder of 5 cm diameter, a 4 hour drying time is adequate. The samples ranged in weight from 50-70 g, had a diameter of 5 cm and a length from about 2 to about 3 cm.
A typical treating liquid was prepared in the following proportions: 25 g of boric acid with the addition of 2 g aluminum acetate boric, 2 g calcium acetate and 0.5 g calcium carbonate in 100 ml of aqueous solvent.
Alternative additives were selected from acetate boric+calcium carbonate; colloidal alumina alone; acetate boric alone; colloidal alumina+calcium acetate; colloidal alumina+calcium oxide; acetate boric+calcium oxide; colloidal silica alone; powdered metal alone and mixtures thereof. The total additive was kept about at 4.5 g, i.e. just below ⅕th the amount of boric acid.
The liquid was heated to 85° C. and mixed until all of the additives were dissolved. Then 0.1 wt % of a surfactant agent (for example, QUAFIN-CT available from Henkel), was added and mixed for 1 minute. Addition of this surfactant may cause foaming and odor. Both can be avoided by adding an anti-foaming agent before or after the addition of the surfactant. The odor can be avoided without addition of the anti-foaming agent if the surfactant is added prior to the heating. Preferably, the anti-foaming agent is added in an amount about equal to that of the surfactant.
The anode sample is then immersed in the liquid at 85° C. For this purpose, the overall volume of the treating liquid must preferably be five times greater than the anode sample and the sample must preferably be able to be totally immersed in the liquid. Upon immersion, bubbling is observed. The immersion time is dependent on the sample size. A 5 to 10 minute immersion time is recommended for a 3 cm long cylinder of 5 cm diameter. Alternatively, the treating liquid may be steamed onto the anode sample using a commercially available steam "cleaner".
The sample is then removed from the liquid and placed in a furnace at 180-200° C. for a drying time dependent on the sample size. A 4 hour drying time was sufficient for a 3 cm long cylinder of diameter 5 cm.
Several samples were prepared as above, varying the liquid composition and the impregnation time and/or method. Samples where the additive was omitted are referred to as "boron-only". The treated samples and several untreated commercial carbon anode blocks of similar sample size were then subjected to the following test procedures.
An oxidation resistance test was performed in a static oxidation condition. The sample surface area and weight were measured before the sample was placed in the furnace and the weight change was measured after certain holding times. The static oxidation test was conducted at a controlled temperature of 500° C., 600° C. or 800° C.±5%; the duration of the exposure varied from 6-150 hours.
The tensile strength of the samples was determined using a method called the diametral compression test. The test is based on the state of stress (F) developed when a cylindrical sample is compressed between two diametral opposite forces, to determine the maximum diametral tensile stress (ST), which acts on the loaded diameter during the test up to failure. At failure, the diametral tensile strength can be calculated according to ST=2F/πhD. The diameter to height ratio D/h typically ranges between 1.5 and 2.
An Instron-4206 machine was used to measure the diametral maximum stress of the treated and untreated samples. The cross head loading speed was kept at 0.1 mm/min. constant rate.
The diametral compression test was carried out on the samples after a given measured weight loss recorded in the oxidation test procedure.
Untreated anodes showed severe weight loss after 20 hours at temperatures higher than 500° C. The weight loss is influenced by temperature and time. After passage of certain time period, the oxidation rate increases sharply. Oxidation occurs on the petroleum coke and pitch (bonding phase) and the sharp increase in oxidation rate is due to the loss of the bonding phase which increases the weight loss. For the untreated samples, the weight loss was so great it could not be effectively measured.
At 500° C., the boron-only impregnated samples show a negligible weight loss in a short term oxidation test (6 or 12 hours). However, in a long term oxidation test (500° C. for 150 hours or 600° C. for 15 hours, the samples showed a significant strength loss associated with the weight loss. These boron-only impregnated samples thus showed a much lower weight loss, than untreated samples but the lower weight loss was associated with a higher strength loss as a function of the weight loss.
From this data it is deduced that with the boron-only impregnated samples, oxidation occurs mostly at the pitch location (bonding phase), which, with time, reduces the overall mechanical strength. After a certain time and temperature, when the weight loss reaches a critical amount (about 8-10% weight loss), corresponding to the brittleness limit, the sample starts to disintegrate.
The strength of the untreated and boron-only treated samples is plotted in FIG. 1 as a function of the percentage weight loss. It can be seen from this graph that the boron-only treated samples B progressively lose strength with increasing weight loss compared to the untreated samples U, it being understood that the boron-only treated samples are nevertheless advantageous due to the fact that they exhibit much improved oxidation resistance. At a given weight loss, about 8 wt % in this example, the boron-only treated samples reach the brittleness limit and are subject to failure, as indicated by F. Commercial pre-baked anodes must be in service for about 30 days, during which service period the observed strength loss becomes a factor for the loss of anode material.
FIG. 2 is a similar graph to which have been added results with samples impregnated with alumina and/or calcium compounds according to the invention. All of these samples showed improved oxidation resistance compared to the boron-only impregnated samples, as well as improved strength as discussed above. The improved strength over the anode lifetime coupled with the improved oxidation resistance procured by the invention significantly improve the performance of anodes impregnated according to the invention over their service life.
The individual components of the additives for the plotted points were as follows:
1. aluminum acetate boric+calcium carbonate
2. colloidal alumina
3. aluminum acetate boric
4. colloidal alumina+calcium acetate
5. colloidal alumina+calcium oxide
6. aluminum acetate boric+calcium oxide
The steam application method described above, results in greatly improved oxidation weight loss for anodes at 600° C., as compared to untreated anodes and anodes treated by the dipping method (using the same treating liquid used for steaming), as shown below in Table 1:
Oxidation Rate of the Steam and Dip Treated Anodes at 600° C.
Commercial Anode
Weight Loss
Weight Loss
Weight loss
The results from Table 1 may be seen in the form of a graph in FIG. 3. Aside from the improved oxidation resistance, the steam method may be used for treating components which are already installed in an aluminum production cell (as opposed to new components for which dipping is possible). Additionally, preheating of the component (drying), of the substrates, which is usual for the dipping method, is not necessary for the steam method.
|Cited Patent
|Filing date
|Publication date
|Aug 21, 1973
|Apr 29, 1975
|Snam Progetti
|Process for the treatment of amorphous carbon or graphite manufactured articles, for the purpose of improving their resistance to oxidation, solutions suitable for attaining such purpose and resulting product
|Jan 10, 1996
|May 19, 1998
|Moltech Invent S.A.
|Carbon bodies resistant to deterioration by oxidizing gases
|Sep 15, 1997
|Nov 16, 1999
|Moltech Invent S.A.
|Carbon bodies resistant to deterioration by oxidizing gases
|Aug 30, 1996
|Dec 14, 1999
|Moltech Invent S.A.
|Application of refractory borides to protect carbon-containing components of aluminium production cells
|Title not available
|May 28, 1993
|Dec 23, 1993
|Moltech Invent S.A.
|The application of refractory borides to protect carbon-containing components of aluminium production cells
|Jun 1, 1994
|Dec 8, 1994
|Moltech Invent S.A.
|Treating prebaked carbon anodes for aluminium production
|U.S. Classification
|429/477, 427/113, 502/101, 427/126.1, 429/535, 429/502
|International Classification
|Cooperative Classification
|European Classification
|May 27, 2000
Owner name: MOLTECH INVENT SA, LUXEMBOURG
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CINCINNATI, UNIVERSITY OF;DE NORA, VITTORIO;DURUZ, JEAN-JACQUES;REEL/FRAME:010869/0130;SIGNING DATES FROM 19970401 TO 20000522
|May 30, 2000
Owner name: CINCINNATI, UNIVERSITY OF, OHIO
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SEKHAR, JAINAGESH A.;LIU, JAMES JENQ;REEL/FRAME:010884/0369
Effective date: 19970401
|Aug 28, 2001
|Certificate of correction
|Dec 18, 2001
|Certificate of correction
|Aug 2, 2004
|Fee payment
Year of fee payment: 4
|Sep 8, 2008
|Maintenance fee reminder mailed
|Feb 27, 2009
|Lapse for failure to pay maintenance fees
|Apr 21, 2009
|Expired due to failure to pay maintenance fee
Effective date: 20090227

subset: commoncrawl


text:
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CINTAA finally apologises to Rakhi Sawant and Dolly Bindra in relation to Pratyusha Banerjee's suicide case Rakhi Sawant to play eunuch in movie Upeksha, shooting kicks off!! Rakhi Sawant Hot & Sexy Photos Happy birthday Rakhi Sawant: Check out ...Bollywoodlife.com, 5 days ago Pratyusha Banerjee case: After threatening to ban Dolly Bindra and Rakhi Sawant, CINTAA joint secy apologises! DNA, 6 days ago CINTAA's Amit Behl apologises to Rakhi Sawant, Dolly Bindra Prokerala, 1 week ago Amit Behl of CINTAA apologises to Rakhi Sawant, Dolly Bindra ABP Live, 6 days ago
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Sachin, Rahman, Bindra approached to be ambassadors for Rio Olympics
Amid raging debate over the choice of Bollywood superstar Salman Khan as India's goodwill ambassador for Rio Olympics, the Indian Olympic Association has approached cricket legend Sachin Tendulkar and oscar-winning music composer A R Rahman, Olympic ...Hindustan Times, 5 days ago Sachin likely to replace Salman MSN News US, 5 days ago
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New Dominion Finance trial underway
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A new trial for three men accused of theft over the collapse of Dominion Finance has begun in the High Court at Auckland.
Former director Robert Whale, former chief executive Paul Cropp and a third man who has name suppression face charges under the Crimes Act of theft by a person in a special relationship.
Three days into the first trial last week Justice Pamela Andrews was forced to step down due to a "perceived bias" towards Whale. Both she and Whale were partners at law firm Kensington Swan.
A new trial began this morning before Justice Graham Lang.
Crown prosecutor Brian Dickey did not re-deliver his opening address, however lawyers for the accused restated their defences.
Dominion Finance failed in September 2008 owing $177 million to more than 5900 debenture holders, and another $56 million to ASB and Bank of Scotland International.
The Crown says the charges arise from the failure of Dominion Finance and its sister company North South Finance, and the case revolves around the issuing of loans to parties related to Dominion Finance's directors.
The proceedings follow an investigation by the Serious Fraud Office. Whale faces five charges of theft, Cropp faces four charges and the other man faces three charges.
The Crown says the three men entered into "unauthorised and highly imprudent related party transactions" in breach of the finance companies' trust deeds.
Before the first trial was aborted the court heard about a Remuera property development involving former rugby league star Matthew Ridge.
In 2002 Ridge's property development company M3 Developers had secured a $2.58m loan from Dominion Finance to buy the land for an 11-apartment complex in Bassett Road, but the project stalled.
The court heard that by 2004 $6m was owed and Ridge was looking to sell the development.
Dominion director Terence Butler organised a sale of the development to a third party, John Williams, who he then formed a joint venture with, and a further $6.6m in loan funding was secured from Dominion, the court was told.
Butler's joint venture relationship with Williams was not declared and the lending increased over the following years to over $8.2m.
The court also heard that Dominion had allegedly used North South Finance - which it bought in 2006 and had the same directors and management - to fund other instances of related-party lending.
However the lawyer for Whale, Paul Davison QC, told the court this morning that his client had no knowledge of the finance companies' trust deeds and there was no intention to act in contravention of them.
"Mr Whale relied upon others within the company to adhere to the requirements of the trust deed," Davison said.
Cropp's lawyer John Billington QC also told the court his client did not intentionally deal with investors' funds against the trust deeds' requirements.
- BusinessDay.co.nz
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Crafty freedom campers using social media to avoid getting caught


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Lyrics Depot is your source of lyrics to It Keeps Slipping My Mind by Tammy Wynette. Please check back for more Tammy Wynette lyrics.
It Keeps Slipping My Mind Lyrics
Artist: Tammy Wynette
Album: Stand By Your Man
I keep intending to tell you I been lonely much too long
And some morning you will wake up and find the note that says I'm gone
I've tried so long to say I'm moving to greener pastures down the line
I keep intending to tell you but it keeps slipping my mind
I've got it on my lips to warn you I've been lonely my last time
And when you wake up in the morning you'll find me gone and lose your mind
I'd like to say that I'll be moving...
I would have --- thinking of the words I'll say
If I could keep old memories from always headin' in my way
I've come so very close to saying my lovin' is a waste of time
I keep intending to tell you but it keeps slipping my mind
Tammy Wynette Lyrics
Tammy Wynette Stand By Your Man Lyrics
More Tammy Wynette Music Lyrics:
Tammy Wynette - Crying Steel Guitar Lyrics
Tammy Wynette - Don't Liberate Me (love Me) Lyrics
Tammy Wynette - Good Lovin' (makes It Right) Lyrics
Tammy Wynette - If This Is Our Last Time Lyrics
Tammy Wynette - Marriage On The Rocks Lyrics
Tammy Wynette - Me And Jesus Lyrics
Tammy Wynette - Together We Stand (divided We Fall) Lyrics
Tammy Wynette - Yearning (to Kiss You) Lyrics


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The Catholic Mobilizing Network is happy to promote events that promote dialogue and common action to end the use of the death penalty in the United States. Please submit events to email@example.com for inclusion on our website and for consideration for publication in our monthly e-newsletter. We encourage you to submit events at least four weeks before they are scheduled to occur. Not all events will be published due to time, space and other concerns.
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- Justice Breyer issues another scathing critique of the #deathpenalty, this time in #California. https://t.co/5dDXF1t5vK about 8 hours ago


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text:
|Name: _________________________
|Period: ___________________
This quiz consists of 5 multiple choice and 5 short answer questions through Chapters 15 and 16.
Multiple Choice Questions
1. What was the name of the tour guides first and only boyfriend?
(a) She has never had a boyfriend.
(b) Colin.
(c) Hassan.
(d) Dewey.
2. What does Colin overhear Hassan and Lindsey discussing?
(a) About Lindsey's plan to break up with her current boyfriend.
(b) About Hassan's attraction to Colin's sister.
(c) About Hassan not wanting to go to college.
(d) Him.
3. Who joins in the effort to help the situation in the graveyard?
(a) One of Lindsey's boyfriend's friend.
(b) Matthew.
(c) No one.
(d) Katrina.
4. Why do the boys stop at a convenience store?
(a) To ask directions to the cemetery.
(b) They see an advertisement for a free map.
(c) It is where the start of the grave is.
(d) They see an advertisement for free gas.
5. What role does the clerk at the convenient store play besides as cashier?
(a) Cook.
(b) Mechanic.
(c) Gas pumper.
(d) Tour guide.
Short Answer Questions
1. What do Hassan and Lindsey decide to play?
2. What does Hassan record with the machine they have been using for interviews?
3. Why do Colin and Hassan use some chewing tobacco?
4. When does the tour guide say she will return?
5. What does Colin tell his parents when he calls them?
This section contains 277 words
(approx. 1 page at 300 words per page)


text:
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Virtual Boy Games
Cat boxer for Telero BoxerHome / Virtual Boy /
This page contains Telero Boxer Hints for Virtual Boy called "Cat boxer" and has been posted or updated on Aug 30, 2006 by sarahbear87.
Boxshot & Details
- Developer: Nintendo
- Publisher: Nintendo
- Genre: Sports
- Release: Not Set
- ESRB: Not Set
Cat boxer
Obtain a perfect record by defeating every boxer with no losses to face a boxer that resembles a cat.
Report Problem
Please submit a problem for any incomplete, non-working or fake cheat listed above.
More Hints
From: saberwolf00
From: jaser66
From: imp14
From: leelee5485
From: sarahbear87
Back to all Cheats
From: ngihtsky
Stuck in this game? Set a specific, clearly defined question and let other gamers answer your question or view answers to previously asked questions. If you think you are an expert then please try to help others with their questions.
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Telero Boxer - Speed Run (TAS)
- Aug 3, 2014, Views: 76
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2003 Lexus GS 300 for Sale in Portland, OR
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2003 Lexus GS 300 Base Review
|by Jack
To sum up this car: It was born out of Toyota engineering in the 90's. Some say some of the best Toyotas were produced then, this car is no exception. With the mighty 2JZ under it's hood and classic Japanese suspension to keep it on the road this car is excellent. And because it is a Lexus no Luxury has been spared, 6 CD player, in-dash touch s...
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2004 Lexus GS 300 Base Used Cars in Milwaukie, OR 97222
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$13 ABOVEInstant Market Value of $7,768
Price: $7,781
Mileage: 171,993
Location: Milwaukie, OR 97222
Average time on market: 35 days Certified Pre-Owned: No Transmission: Automatic Color: Mystic Sea Opalescent Description: Used 2004 Lexus GS 300 Base for sale - $7,781, 171,993 miles with Navigation System, Sunroof/Moonroof, Alloy Wheels
Avg. Dealer Rating: (28 reviews) "Good service and staff. Great experience. No pressure. I would recommend Speed Sprots dealership."
2002 Lexus GS 300 Base Used Cars in Portland, OR 97233
Fair Deal
$281 ABOVEInstant Market Value of $7,719
Price: $8,000
Mileage: 126,000
Location: Portland, OR 97233
Average time on market: 18 days Certified Pre-Owned: No Transmission: Automatic Color: Green Description: Used 2002 Lexus GS 300 Base for sale - $8,000, 126,000 miles with Alloy Wheels
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