US3925001A - Placement of catalytically active materials in combustion flames - Google Patents

Placement of catalytically active materials in combustion flames Download PDF

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US3925001A
US3925001A US098338A US9833870A US3925001A US 3925001 A US3925001 A US 3925001A US 098338 A US098338 A US 098338A US 9833870 A US9833870 A US 9833870A US 3925001 A US3925001 A US 3925001A
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flame
zirconium
manganese
fuel
reaction zone
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Kailish Chander Salooja
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C13/00Apparatus in which combustion takes place in the presence of catalytic material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23CMETHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN  A CARRIER GAS OR AIR 
    • F23C13/00Apparatus in which combustion takes place in the presence of catalytic material
    • F23C13/08Apparatus in which combustion takes place in the presence of catalytic material characterised by the catalytic material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23DBURNERS
    • F23D11/00Burners using a direct spraying action of liquid droplets or vaporised liquid into the combustion space
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/08Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases using flares, e.g. in stacks
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23GCREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/08Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases using flares, e.g. in stacks
    • F23G7/085Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases using flares, e.g. in stacks in stacks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90Regeneration or reactivation

Definitions

  • ABSTRACT Combustion of a carbonaceous fuel in a flame is img 431/4 431/347 proved by placing a catalyst comprising a metal or I n n u u u u u u e s s n l u I n e n l l I o e e s l l I u I e I l I I on t l I Field of ch IIIII u 326, 50, 351; me al oxide in the prlmary reaction zone and thereby reducing smoke formation.
  • FIG. 7. P23 21 22 US. Patent Dec. 9, 1975 Sheet 2 of6 3,925,001
  • Carbon-containing materials such as natural gas, liquid petroleum hydrocarbons and solid carbonaceous fuels are combusted with air or oxygen to provide heat and/or power.
  • air or oxygen In most instances of such combustion, efforts are made to derive thehighest combustion temperatures by employing the minimum quantities of air (or oxygen) but in the interests of efficient utilization of the heat value of the fuel, it is necessary to provide an excess of air or oxygen over the stoichiometric requirement. The excess air lowers the temperature of the combustion gases but ensures that the overall heat output is increased and that the amount of non-combusted material which appears as smoke is reduced.
  • the smoke represents a wasted resource, is a potential ficult it is to effect heat transfer from the combustion gases, in the case of boilers and furnaces, while in the case of heat engines, the thermodynamic efficiency is reduced.
  • the use of additives in the fuel which pass with the fuel into the flame, and pass through the flame the additives or derivatives of the additivescan be detected in the resulting combustion gases, and in some cases contribute to the polluting nature of the combustion gases.
  • a very hot zone termed the primary reaction zone, adjacent the base of the flame in which combustion proceeds vigourously and in which the concentration of ions is at a maximum in the flame.
  • a secondary reaction zone downstream of the primary reaction zone which contains the most luminous part of the flame.
  • catalysts which are found to be useful are metals,- metal oxides and compounds which decompose under heat to metals and metal oxides, and metal salts which are substantially stable at high temperatures.
  • Specific examples of catalysts are barium, magnesium, iron, tin, aluminium, vanadium, manganese, sodium, calcium, zirconium, platinum, yttrium, lanthanum, erbium, gallium,.titanium, chromium, cobalt, nickel, palladium, rare earth metals other than those hereinbefore specified, oxides of any of .the foregoing metals, compounds which decompose to oxides of the foregoing metals under the action of heat, and heat stable compounds of said metals. It will be appreciated from the foregoing that many other metal compounds may be employed.
  • synergistically effective combinations are the metals, oxides or heat stable compounds of: barium and sodium, barium and yttrium, barium and erbium, barium and zirconium, aluminium and sodium, aluminium and yttrium, aluminium and lanthanum, aluminium and erbium, aluminium and platinum, gallium and sodium, zirconium and yttrium, zirconium and erbium, zirconium and chromium, zirconium and manganese, zirconium and iron, zirconium and platinum, manganese and sodium, manganese and yttrium, manganese and titanium, manganese and chromium, manganese and iron,-manganese and nickel and palladium and iron.
  • the metals, oxides or heat stable compounds of: barium and sodium, barium and yttrium, barium and erbium, barium and zirconium, aluminium and sodium, aluminium and yttrium,
  • the invention is distinguished from prior expedients to mitigate smoke formation in that substantially none of the catalyst is found in the combustion gases. Moreover, the combustion of flames in contact with materials which are catalytically active for reducing smoke has previously been carried out with the said materials contacting either the whole flame or the secondary zon'e thereof, but it has not previously been proposed that contact between the flame and any particular material or materials shouldbe confined to the primary reaction zone of the flame.
  • the catalyst be located within the primary reaction zone as far as possible upstream from the secondary reaction zone, and near to, but within the base of the flame, so that the risk of contact of the secondary zone withthe catalyst is minimized.
  • the catalyst may be provided in the form of wires or a planar mesh or grid, or a flat spiral, or cylindrical coil, of wires or a perforated screen, the wires or screen being either of the catalyst itself or of a supporting material which is composited with or on which is coated the catalyst.
  • the catalyst may be impregnated onto asbestos or like flame resisting porous material.
  • a convenient method'of making the supported form of catalyst is to impregnate the support with a solution of a suitable metal compound, dry the impregnated support of solvent and to heat the support until the metal compound or a heat stable derivative thereof is effectively bound to the support.
  • the form in which the catalyst is provided should be such 3 that it causes a minimum of disturbance to the flow of fuel and air and to the general aerodynamics of the flame.
  • the benefits arising from the invention include, as a result of the use of less excess air than would otherwise necessarily be the case, not only a higher thermodynamic efficiency, but also the possibility of burning fuel at greater rates without producing smoke in a given volume, and thereby increasing the maximum power output from a boiler, furnace or engine.
  • the fuel employed contains sulphur (which is usually the case)
  • the reduced excess air reduces the proportion of corrosive sulphur trioxide in the combustion gases which is produced by oxidation of sulphur dioxide: similarly, because there is less excess air, the proportion of undesirable oxides or nitrogen tends to be reduced.
  • FIG. 1 illustrates diagrammatically a method of locating the various reaction zones of a flame.
  • FIG. 2 illustrates schematically an apparatus employed for investigations in connection with the present invention.
  • FIG. 3 shows an investigation in connection with this invention being effected using the apparatus of FIG. 2.
  • FIG. 4 is a cross-sectional elevational view of the principal parts of a domestic central heating burner.
  • FIG. 5 is a perspective view of a flame plate assembly forming part of the burner of FIG. 4.
  • FIG. 6 shows perspectively a mesh or grid of catalytically active material for use with the burner of FIG. 4.
  • FIG. 7 shows the lower part of the burner of FIG. 4 and the general structure of a typical flame therefrom.
  • FIG. 8 shows a conventional refinery flare stack.
  • FIG. 9 is a perspective view of a form of catalyst for use with refinery flares.
  • FIG. 10 depicts perspectively the embodiment of FIG. 9 mounted on a refinery ground flare or stack
  • FIG. 11 illustrates the mode of action of the embodiment of FIG. 10.
  • FIG. 1 there is shown a burner tube through which a fuel, such as an inflammable gas, is passed.
  • a fuel such as an inflammable gas
  • the gas is combusted to form a flame 23 and electrodes 21, 22 are located with their free ends in diametrically opposed parts of the visible edge of the flame 23.
  • the ends of the electrodes 21, 22 are rounded to a known radius so that the area of electrode available for ion collection is known: a suitable radius is 0.5 mms. for electrodes I mm. diameter.
  • a voltage is applied across the flame 23 from the electrodes 21, 22, the voltage being supplied from a battery 24 and regulated by a tapping 25 of a potentiometer 26. The voltage is measured by a voltmeter 27 and the current passing through the flame by a micro-ammeter 28.
  • the voltage applied across the flame 23 is progressively increased for each location of the flame until a saturation current is reached indicating that for that location, the maximum current for the ionic concentration has been reached.
  • the current direction is reversed by a switching device (not shown) to compensate for any assymmetry in the flame, and the procedure repeated. The whole procedure so far described is repeated for a number of positions of the electrodes 21, 22 in the flame 23 until a profile of the ion concentration for the flame can be constructed.
  • the region of the flame nearest to the burner tube 20, apart from a cool fuel and air mixing zone 29 has the highest ion concentration, this being the so-called primary reaction zone.
  • the primary reaction zone is always adjacent to the base of the flame 23, and terminates fairly abruptly at locations distal from the base of the flame: the region of the flame which is furthest from the base of the flame is found to be of low conductivity, and contains the most luminous part of the flame.
  • the various zones found by the method described in relation to FIG. 1 are indicated by I which is the primary reaction zone extending from the cool base of the flame at the top of the burner 30, II which is the secondary reaction zone which, with the cool zone, sandwiches the primary reaction zone, and III a cooler tertiary zone wherein smoke (if any) tends to be visible to the eye.
  • the various zones of the flame 40 are not intended to be shown in the correct relative sizes in FIG. 2.
  • FIG. 3 shows a test for smoke mitigation in accordance with the invention using the apparatus of FIG. 2.
  • the test procedure is as follows in a typical case, given by way of Example.
  • EXAMPLE 1 Test (a) Ethylene gas from the cylinder (not shown) was passed through the rotameter 33 of FIG. 3, premixed with a small known fixed flow rate of air measured by the rotameter 37 of FIG. 2 and passed to the barrel of the upright tubular burner 30. A measured fixed flow rate of secondary combustion air was passed into the annular space between the burner 30 and the glass tube 41, and maintained throughout the tests at 400 cc s/minute.
  • the effect of a catalyst in accordance with the invention was now investigated.
  • the chosen catalyst was barium oxide coated onto a circular filament of quartz at one end of a quartz rod, as depicted in FIG. 3.
  • Test (c) The coated filament 47 was positioned within the flame just above the barrel of the burner tube 30 and in the bluish-coloured primary reaction zone (zone I of FIG. 2).
  • the coated filament 47 was located at the top (zone III of FIG. 2) of the visible flame with an ethylene-air flow rate of 94 ccs per minute. No effect on the amount of smoke was observed, and an increase in the ethylene flow rate increased the amount of smoke in the same way as in the absence of the filament 47.
  • the tests (a), (b), (c) and (d) illustrate the criticality of the location of the catalyst in the flame.
  • the tests also demonstrate in a simple way that by the practice of the invention, the proportion of excess air in relation to the fuel consumed necessary for the satisfactory combustion of a fuel can be reduced thus improving the efficiency of combustion.
  • Example 2 The test of Example 1 were performed again but with ethylene premixed with a fixed quantity of air (from line 35 in FIG. 2), the air flow rate being again 21.5 ccs/minutes, and the amount of secondary air again being fixed at a flow-rate of 400 ccs/minute.
  • the filament 37 of FIG. 3 was coated with different metal oxides in each test, and starting with an ethylene flow-rate of 94 ccs/minute to give a flame in which smoke formation was about to occur at the top, the percentage increase in the rate of ethylene flow with each coated filament located in the primary reaction zone of the flame, relative to the fuel flow rate in the absence of the coated filaments, being noted.
  • the burner is shown in FIG. 4 and was of the downwardly-firing type that is to say, the flame extended downwards from the burner.
  • the burner 50 comprised a fuel pump 51, a central tube 52 for the fuel which terminated at its lower-most end in a nozzle 53 having number of fine orifices for atomising the fuel, a centrifugal fan 54 for supplying primary combustion air and a concentric tube 55 for primary combustion air surrounding the fuel tube 52.
  • the concentric tube 55 extended slightly lower than the central fuel tube 52, and a flame plate extended across the bottom of the air and fuel tubes 55, 52 respectively. Ignition of the mixture of air and atomized fuel was effected by means of an electrode 56 carried by an insulated support.
  • the flame plate is shown in more detail in FIG.
  • the flame plate is supported by a number of struts 64 which extend from the upper side of the support ring 57 to a fixed ring located around the fuel tube 52.
  • the burner 50 is set into a refractory wall 58 at its downstream side, and a stout strut 59 attached to the outside of the air tube 55 provides lateral support for the burner 55.
  • a catalytically active grid 66 shown in FIG. 6, was made up by forming in a ring 60 of 4% inches diameter a refractory mesh or network of 1/16 inch thick wire like members forming individual rectangles of 1 inch by 72 inch. A layer of barium oxide was coated on the wires of the grid to bring the thickness of the wires to about 7% inch. On diametrically opposite outer sides of the ring 66 were provided supporting lugs having internally threaded holes for the receipt of locating screws.
  • the burner was ignited in the normal way and the air flow rate was monitored. During normal operation, the excess air was found to be about 20% for the selected fuel flow-rate.
  • Flg. 7 shows the general form of flame produced below the burner.
  • the flame base was located about Vs inch below the flame plate, and the flame itself extended about -12 inches below the flame plate and was 3% to 4 inches in diameter
  • the relatively high velocity of the swirling fuel and air mixture passing from the flame plate made the primary reaction zone boundaries somewhat indeterminate by visual observation, but it was expected that the primary reaction zone would not extend much more than about 1% 1% inches from the flame plate, the secondary reaction zone accounting for most of the rest of the flame.
  • the catalyst grid 66 of FIG. 6 was disposed in the flame at various distances from the flame plate, which was used as a reference for distance.
  • the burner support wall 58 is provided with apertures through which depend captive screws 69 held in position by washers 70 around a neck of the screws 69.
  • the captive screws 69 are so arranged that they can engage with the threaded holes in the lugs 68 of the grid 66 and by rotation of the screws 69, the distance between the plane of the mesh or network of coated wires 67 and the flame plate can be adjusted.
  • the amount of smoke generated by the flame was determined by the Standard Bacharach test.
  • results in the table demonstrate that a marked reduction in smoke and hence an improvement in fuel utilization is obtained by disposing the catalyst near the base of the flame (i.e., near the flame plate), and in the region of the primary reaction zone of the flame.
  • Example 3 Although the above tests of Example 3 were performed on a domestic boiler, it will be appreciated that the benefits of the invention can be realized on larger boilers, and that due to the lower excess air requirements, benefits such as smaller air fans, pipes and combustion chambers can be realized with considerable savings in cost.
  • the reduction in SO concentration would be beneficial in respect of less corrosion, and in nitrogen oxides in less atmospheric pollution.
  • the decrease in smoke would of course lead to less frequent shut-downs of industrial plant for cleaning.
  • a particularly useful application of the invention is to the mitigation of smoke formation in the burning of petroleum refinery waste hydrocarbon gases. These gases are of variable composition and their quantity often varies: accordingly, they have little value and their disposal is most simply accomplished by burning them in flares which are commonly at the top of tall flare stacks, and sometimes nearer to the ground on socalled ground stacks.
  • FIG. 8 shows the essential features of a conventional flare stack arrangement wherein the stack 81 is supplied with waste refinery gases by a trunking 82, and the gases are burned in a flame 84 at the top of the stack 81.
  • the flame may be 60 feet in length, sometimes more, any may produce large quantities of smoke, depending on the composition of the gases.
  • steam injection steam is injected into the stack 81 through a trunking 83.
  • One form of catalyst for refinery flare use in accordance with the invention is a cylindrical coil of alumina-silica material previously impregnated with a mixture of barium and sodium compounds such as barium nitrate and sodium hydroxide and fired to convert the barium nitrate to barium oxide and to dehydrate to some extent, the sodium hydroxide to sodium oxide which combines with the ceramic. It has been found that the cylindrical coil stablized flames, and promoted the induction into the flare flame of secondary air which enhanced the smoke reducing activity of the barium, sodium and alumina containing coil.
  • a suitable cylindrical coil 90 is shown in FIG. 9.
  • the coil has a mean diameter slightly exceeding the diameter of the flare exit, and a length preferably no greater than 20% of that of the expected mean length of the flame and more preferably, up to of the flame length.
  • EXAMPLE 4 In a qualitative experimental simulation of the application of the invention to flare stack operation, a tube of approximately 1% inches internal diameter represented the flare stack, and the fuel was a mixture of saturated hydrocarbon gases known in the art as LPG (liquified petroleum gas) enriched with propene to cause smoke formation. The rate of gas flow was so adjusted that a smokey flame having a height of 4 to 5 feet was obtained.
  • LPG saturated petroleum gas
  • a cylindrical barium/sodium/silica-alumina coil made as described above having the form shown in FIG. 9 with dimensions of about 1% inches internal diameter and about 9 inches long was inserted into the base of the flame.
  • the invention is useful in windy conditions when the axis of the flame is inclined to the vertical or even substantially horizontal.
  • the catalyst coil be mounted, e.g., on gimbals, for rotational movement about a vertical axis and rotational movement about a horizontal axis, there being at least one wind vane device attached directly or indirectly to the catalyst coil to maintain the catalyst coil within the primary reaction zone of the flame and with the axis of the coil and the flame substantially coincident.
  • FIG. 9 illustrates a way of applying the practice of the invention to refinery flares, and the stack 81 may be of the type shown in FIG. 8 or it may be of the ground flare type.
  • a collar 91 Attached near the top of the stack 81 is a collar 91 on which is rotatably mounted a ring 92 which is suitably separated from the collar 91 by bearings, diagrammatically shown as rollers 93. It is also preferred to provide bearings (not shown) between the ring 92 and the stack 81. The form of the appropriate bearings will be clear to those skilled in the art.
  • a wind vane 94 responsive to changes in the horizontal component of wind direction is attached to the ring 92 so that changes in wind direction in horizontal planes cause rotation of the ring 92.
  • stub axles 95 which project outwardly from the ring on diametrically opposed sides thereof.
  • Each stub axle 95 serves to support in a recessed journal-bearing a rod 96 having a bearing collar 97.
  • a counterweight 98 which serves to maintain the rod 96 in the position illustrated.
  • a wind vane 99 is formed in each rod 96 above the collar 97, the vanes 99 being at right angles to the vane 94 and responsive to changes in the vertical components of wind direction.
  • a coil 90 of the type illustrated in FIG. 9, is located relative to the stack 81 by horizontal rods extending inwardly from the tops of rods 96, the rods 100 being attached to the coil 90.
  • the flare flame encloses the coil 90 and burns vertically, the coil 90 helping to diffuse air into the flame and additionally stabilizing the flame.
  • the mitigation of smoke may be so great that steam injection may be dispensed with entirely.
  • the vane 94 causes the ring 92 to rotate to a position in which the vanes 99 are substantially perpendicular to the wind direction, and the wind, then acting on the vanes 99 against the action of the counterweights 98, causes the coil 90 to be tilted substantially into the flame 101.
  • the flame stabilizes around the coil, and, by the principles of the present invention, smoke produced by the flame is substantially reduced or eliminated.
  • EXAMPLE 5 The experiments described in examples 1 and 2 and illustrated diagrammatically in FIGS. 2 and 3 were performed with mixtures of metal oxides coated on the quartz filament 47.
  • the fuel was again ethylene premixed with a fixed flow-rate of air (21.5 ccs per minute) and with a fixed flow-rate of secondary air (400 ccs per minute).
  • a mixture of metal oxides such as the mixtures disclosed in table 2 are located in the primary reaction zone of the flame of a domestic or industrial burner, or in the flame of a refinery gas flare, or in the flames from blast furnace gases or flames for the firing of limestone, ceramics and bricks.
  • the invention is also useful in engines wherein there is a reasonable degree of definition of the primary reaction zone of the flame e.g., in external combustion engines and in the cans of the combustion chambers of gas-turbine engines.
  • the invention may also be useful in certain types of diesel engine wherein the initial combustion of the fuel is effected in a cell which is separated from the main combustion chamber.
  • a method of improving the combustion of a carbon-containing fuel in a flame comprising fixedly disposing in the primary reaction zone characterized by the flame having its highest ion concentration, a solid material which is catalytically active for reducing smoke and which is substantially involatile at the temperature of the primary reaction zone, wherein the catalytically active material is selected from the combination of compounds of barium and sodium, barium and yttrium, barium and erbium, barium and zirconium, aluminium and sodium, aluminium and yttrium, aluminium and lanthanum, aluminium and erbium, aluminium and platinum, gallium and sodium, zirconium and yttrium, zirconium and erbium, zirconium and chromium, zirconium and manganese, zirconium and iron, zirconium and platinum, manganese and sodium, manganese and yttrium, manganese and titanium, manganese and chromium, manganese and iron, manganese
  • the catalytically active material is selected from the following metal and metal compounds: barium, magnesium, iron, tin, aluminium, vanadium, manganese, sodium, calcium, zirconium, platinum, yttrium, lanthanum, erbium, gallium, titanium, chromium, cobalt, nickel, palladium, a rare earth metal, oxides of any of said metals, compounds of said metals which decompose to oxides 12 under the action of heat, and heat stable compounds of said metals.
  • Apparatus for burning a carboncontaining fuel comprising means for the supply of a carboncontaining fuel to a combustion zone wherein the fuel is burned in a flame having a primary reaction zone characterized by the flame having its highest ion concentration and a secondary reaction zone having low ion concentration relative to said primary zone, and a solid catalytically active material located in the primary reaction zone of the flame, said solid material being active for reducing smoke and being substantially involatile at the temperature of the primary reaction zone, wherein the catalytically active material is a compound selected from compounds of barium and sodium, barium and yttrium, barium and erbium, barium and zirconium, aluminium and sodium, aluminium and yttrium, aluminium and lanthanum, aluminium and erbium, aluminium and platinum, gallium and sodium, zirconium and yttrium, zirconium and erbium, zirconium and chromium, zirconium and manganese, zirconium and iron, zi
  • the catalytically active material is selected from the following metal and metal compounds: barium, magnesium, iron, tin, aluminium, vanadium, manganese, sodium, calcium, zirconium, platinum, yttrium, lanthanum, erbium, gallium,'titanium, chromium, cobalt, nickel, palladium, oxides of any of said metals which decompose under the action of heat to the oxide.
  • Apparatus for burning a carboncontaining fuel comprising means for the supply of a carboncontaining fuel to a combustion zone wherein the fuel is burned in a flame having a primary reaction zone and a secondary reaction zone, and a solid material having at least part located in the flame, at least a major portion of said part being located in the primary reaction zone of the flame, the said solid material being catalytically active for reducing smoke and being substantially involatile at the temperature of the primary reaction zone, said catalytically active material being in the form of a substantially cylindrical spiral having a mean diameter slightly smaller than the mean diameter of the primary reaction zone.
  • Apparatus according to claim 5 in which the fuel is a gaseous fuel and the said means for the supply of fuel to the combustion zone comprises an upstanding tube having an outlet for gaseous fuel at the top, the said substantially cylindrical spiral being mounted relative to the tube on supports permitting movement of the spiral in three dimensions, and there being means responsive to the wind direction in the vicinity of the top of the tube for causing movement of the spiral relative to the top of the tube whereby the axis of the tube is substantially maintained coaxial with the axis of the flame formed by combustion of the fuel at the top of the tube.

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US098338A 1969-12-19 1970-12-15 Placement of catalytically active materials in combustion flames Expired - Lifetime US3925001A (en)

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CA (1) CA933461A (enrdf_load_stackoverflow)
DE (1) DE2062225A1 (enrdf_load_stackoverflow)
FR (1) FR2074025A5 (enrdf_load_stackoverflow)
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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285666A (en) * 1977-11-10 1981-08-25 Burton Chester G Apparatus and method for increasing fuel efficiency
US4447203A (en) * 1980-11-28 1984-05-08 Hampton William J Flame combustion of carbonaceous fuels
US4781578A (en) * 1984-01-24 1988-11-01 John Zink Company Pilot burner apparatus
US4907964A (en) * 1981-09-29 1990-03-13 Coal Industry (Patents) Limited Device for extracting and burning methane
US4992041A (en) * 1989-11-13 1991-02-12 Gas Research Institute Method and apparatus for producing a wood-like flame appearance from a fireplace-type gas burner
US5070065A (en) * 1990-08-06 1991-12-03 Texaco Inc. Compositions involving V2 O3 -Al2 O3 -CaO
US5124305A (en) * 1990-08-06 1992-06-23 Texaco, Inc. Compositions involving FeO--V2 O3 --CaO
WO1992014043A1 (en) * 1991-02-04 1992-08-20 International Marketing Affiliates Combustion enhancement system
US5202303A (en) * 1989-02-24 1993-04-13 W. R. Grace & Co.-Conn. Combustion apparatus for high-temperature environment
US5260248A (en) * 1992-08-28 1993-11-09 Carus Corporation Stable high temperature manganese based oxidation catalyst
US5328359A (en) * 1992-05-19 1994-07-12 W. R. Grace & Co.-Conn. Ignition stage for a high temperature combustor
US5437099A (en) * 1989-02-24 1995-08-01 W. R. Grace & Co.-Conn. Method of making a combustion apparatus for high-temperature environment
EP0785395A3 (fr) * 1996-01-18 1998-11-25 Fonderies Du Lion S.A. Brûleur à hydrocarbure liquide
US6276287B1 (en) * 1999-05-03 2001-08-21 Toda Kogyo Corporation Iron compound catalyst for inhibiting generation of dioxin and incineration process of municipal solid waste using the same
US20030039932A1 (en) * 2001-08-09 2003-02-27 Advanced Catalyst Systems, Llc Catalytic embers for use with a gas fired log set
US20040025753A1 (en) * 2002-08-08 2004-02-12 Vicat Cement manufacturing processes with a view to reducing NOx emissions in particular
US20060174902A1 (en) * 2005-02-09 2006-08-10 Bing Zhou Tobacco catalyst and methods for reducing the amount of undesirable small molecules in tobacco smoke
US20060228282A1 (en) * 2005-04-12 2006-10-12 Bing Zhou Method for reducing NOx during combustion of coal in a burner
EP1801498A1 (en) * 2005-12-23 2007-06-27 Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO Method for generating radiation
US20070180760A1 (en) * 2006-02-09 2007-08-09 Headwaters Nanokinetix, Inc. Crystalline nanocatalysts for improving combustion properties of fuels and fuel compositions incorporating such catalysts
US7803201B2 (en) 2005-02-09 2010-09-28 Headwaters Technology Innovation, Llc Organically complexed nanocatalysts for improving combustion properties of fuels and fuel compositions incorporating such catalysts
US20100261126A1 (en) * 2007-12-06 2010-10-14 Massimo Malavasi Combustion process
WO2011025613A1 (en) * 2009-08-31 2011-03-03 Rudolf W. Gunnerman Non-fractionation process for production of low-boiling fuel from crude oil or fractions thereof
US20110163007A1 (en) * 2010-01-04 2011-07-07 Gunnerman Rudolf W Non-fractionation process for production of low-boiling fuel from crude oil

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NL9200996A (nl) * 1992-06-05 1994-01-03 Produktcentrum T N O Katalytische brander, alsmede daarvoor geschikte katalysator en katalysatordrager.
FR2735213B1 (fr) 1995-06-12 1997-07-11 Kodak Pathe Procede et dispositif de destruction par incineration de gaz de reaction

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US2014686A (en) * 1931-08-27 1935-09-17 Lubovitch Combustion of fuels
US2259010A (en) * 1939-05-24 1941-10-14 William F Doyle Apparatus for combustion of fluid fuel
US2828814A (en) * 1955-04-12 1958-04-01 Patrol Valve Company Low input pilot burner
US2855770A (en) * 1958-10-14 Device for t

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US2014686A (en) * 1931-08-27 1935-09-17 Lubovitch Combustion of fuels
US2259010A (en) * 1939-05-24 1941-10-14 William F Doyle Apparatus for combustion of fluid fuel
US2828814A (en) * 1955-04-12 1958-04-01 Patrol Valve Company Low input pilot burner

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285666A (en) * 1977-11-10 1981-08-25 Burton Chester G Apparatus and method for increasing fuel efficiency
US4447203A (en) * 1980-11-28 1984-05-08 Hampton William J Flame combustion of carbonaceous fuels
US4907964A (en) * 1981-09-29 1990-03-13 Coal Industry (Patents) Limited Device for extracting and burning methane
US4781578A (en) * 1984-01-24 1988-11-01 John Zink Company Pilot burner apparatus
US5202303A (en) * 1989-02-24 1993-04-13 W. R. Grace & Co.-Conn. Combustion apparatus for high-temperature environment
US5437099A (en) * 1989-02-24 1995-08-01 W. R. Grace & Co.-Conn. Method of making a combustion apparatus for high-temperature environment
US4992041A (en) * 1989-11-13 1991-02-12 Gas Research Institute Method and apparatus for producing a wood-like flame appearance from a fireplace-type gas burner
US5124305A (en) * 1990-08-06 1992-06-23 Texaco, Inc. Compositions involving FeO--V2 O3 --CaO
US5070065A (en) * 1990-08-06 1991-12-03 Texaco Inc. Compositions involving V2 O3 -Al2 O3 -CaO
WO1992014043A1 (en) * 1991-02-04 1992-08-20 International Marketing Affiliates Combustion enhancement system
US5247909A (en) * 1991-02-04 1993-09-28 Advanced Combustion Technologies, Inc. Combustion enhancement system
US5328359A (en) * 1992-05-19 1994-07-12 W. R. Grace & Co.-Conn. Ignition stage for a high temperature combustor
US5406704A (en) * 1992-05-19 1995-04-18 W. R. Grace & Co.-Conn. Method for making an ignition stage for a high temperature combustor
US5260248A (en) * 1992-08-28 1993-11-09 Carus Corporation Stable high temperature manganese based oxidation catalyst
EP0785395A3 (fr) * 1996-01-18 1998-11-25 Fonderies Du Lion S.A. Brûleur à hydrocarbure liquide
US6276287B1 (en) * 1999-05-03 2001-08-21 Toda Kogyo Corporation Iron compound catalyst for inhibiting generation of dioxin and incineration process of municipal solid waste using the same
US6800587B2 (en) 1999-05-03 2004-10-05 Toda Kogyo Corporation Iron compound catalyst for inhibiting generation of dioxin
US20030039932A1 (en) * 2001-08-09 2003-02-27 Advanced Catalyst Systems, Llc Catalytic embers for use with a gas fired log set
US6805115B2 (en) 2001-08-09 2004-10-19 Advanced Catalyst Systems, Llc Catalytic embers for use with a gas fired log set
US20040025753A1 (en) * 2002-08-08 2004-02-12 Vicat Cement manufacturing processes with a view to reducing NOx emissions in particular
US7803201B2 (en) 2005-02-09 2010-09-28 Headwaters Technology Innovation, Llc Organically complexed nanocatalysts for improving combustion properties of fuels and fuel compositions incorporating such catalysts
US20060174902A1 (en) * 2005-02-09 2006-08-10 Bing Zhou Tobacco catalyst and methods for reducing the amount of undesirable small molecules in tobacco smoke
US7856992B2 (en) 2005-02-09 2010-12-28 Headwaters Technology Innovation, Llc Tobacco catalyst and methods for reducing the amount of undesirable small molecules in tobacco smoke
US20060228282A1 (en) * 2005-04-12 2006-10-12 Bing Zhou Method for reducing NOx during combustion of coal in a burner
US7357903B2 (en) 2005-04-12 2008-04-15 Headwaters Heavy Oil, Llc Method for reducing NOx during combustion of coal in a burner
EP1801498A1 (en) * 2005-12-23 2007-06-27 Nederlandse Organisatie voor Toegepast-Natuuurwetenschappelijk Onderzoek TNO Method for generating radiation
US7758660B2 (en) 2006-02-09 2010-07-20 Headwaters Technology Innovation, Llc Crystalline nanocatalysts for improving combustion properties of fuels and fuel compositions incorporating such catalysts
US20070180760A1 (en) * 2006-02-09 2007-08-09 Headwaters Nanokinetix, Inc. Crystalline nanocatalysts for improving combustion properties of fuels and fuel compositions incorporating such catalysts
US20100261126A1 (en) * 2007-12-06 2010-10-14 Massimo Malavasi Combustion process
US9562205B2 (en) * 2007-12-06 2017-02-07 Itea S.P.A. Combustion process for the reduction of particulates in combustion fumes
WO2011025613A1 (en) * 2009-08-31 2011-03-03 Rudolf W. Gunnerman Non-fractionation process for production of low-boiling fuel from crude oil or fractions thereof
CN102597184A (zh) * 2009-08-31 2012-07-18 鲁道夫·W·贡纳曼 从原油或其馏分制备低沸点燃料的非分馏方法
US20110163007A1 (en) * 2010-01-04 2011-07-07 Gunnerman Rudolf W Non-fractionation process for production of low-boiling fuel from crude oil
US8226817B2 (en) 2010-01-04 2012-07-24 Gunnerman Rudolf W Non-fractionation process for production of low-boiling fuel from crude oil

Also Published As

Publication number Publication date
DE2062225A1 (de) 1971-06-24
FR2074025A5 (enrdf_load_stackoverflow) 1971-10-01
CA933461A (en) 1973-09-11
NL7018509A (enrdf_load_stackoverflow) 1971-06-22

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