WO2004026996A1 - Composition d'additif de combustible et sa preparation - Google Patents

Composition d'additif de combustible et sa preparation Download PDF

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Publication number
WO2004026996A1
WO2004026996A1 PCT/SE2003/001446 SE0301446W WO2004026996A1 WO 2004026996 A1 WO2004026996 A1 WO 2004026996A1 SE 0301446 W SE0301446 W SE 0301446W WO 2004026996 A1 WO2004026996 A1 WO 2004026996A1
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WIPO (PCT)
Prior art keywords
oxide
oil
metal
vanadium
fuel additive
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PCT/SE2003/001446
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English (en)
Inventor
Anders Wallenbeck
Gunnar STRÖM
Björn FORSBERG
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Systemseparation Sweden Ab
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Filing date
Publication date
Application filed by Systemseparation Sweden Ab filed Critical Systemseparation Sweden Ab
Priority to EP03797773A priority Critical patent/EP1543094A1/fr
Priority to AU2003261053A priority patent/AU2003261053A1/en
Priority to EA200500499A priority patent/EA010070B1/ru
Priority to US10/528,079 priority patent/US20060059768A1/en
Priority to CA002498151A priority patent/CA2498151A1/fr
Publication of WO2004026996A1 publication Critical patent/WO2004026996A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1216—Inorganic compounds metal compounds, e.g. hydrides, carbides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal

Definitions

  • the present invention relates to a fuel additive composition for the reduction/removal of vanadium-containing ash deposits, a process for the preparation of such a composition and the use of certain inorganic oxygen-containing metal compounds as a component of such a composition. More particu- larly the present invention relates to a fuel additive composition for the reduction/removal of vanadium-containing ash deposits in gas turbines and other by .combustion of vanadium- containing fuel driven apparatuses, a process for its preparation and the use of certain inorganic oxygen-containing metal compounds as an active component thereof.
  • One such impurity is vanadium, which forms catastrophically, corrosive low-melting slag. Said slag can destroy vital parts within a short time.
  • Crude oils usually contain vanadium in an amount within the range of 1-500 ppm depending on the source of the oil. Because of its origin as a concentrate from the refining process, residual oil contains several times more vanadium than the crude from which it is derived.
  • V 2 0 5 vanadium pentoxide
  • V 2 0 5 behaves as an excellent solvent for e.g. the metal oxides that high temperature alloys used in the hot section of gas turbines form in order to protect their surfaces.
  • molten V 2 0 5 acting as a solvent, strips away said metal oxides.
  • the jnetal atoms on the surface of the gas turbine section in contact with the combustion gases respond by forming a new layer of oxide coating which is again stripped away by the V 2 0 5 and so on.
  • metal temperatures can be higher than 1000°C at which temperatures corrosion can proceed very fast so that the hot section may be destroyed within a week if no measures are taken to inhibit the corrosion cycle.
  • oil soluble magnesium products were developed. These products are based on the ability of magnesium compounds to react with V 2 0 5 to form a vanadate. Early products belonging to this group contained magnesium naphthenates which in the next step of development were replaced by compositions based on magnesium sulfonates. The third generation of oil soluble magnesium products comprises magnesium car- boxylate products.
  • US RE 32653 discloses a method for the preparation of a magnesium-containing complex by heating, at a temperature above about 30°C a mixture consisting essentially of (A) at least one of magnesium hydroxide, magnesium oxide, hy- drated magnesium oxide or a magnesium alkoxide; (B) at least one oleophilic organic reagent consisting essentially of an aliphatic cycloaliphatic or aromatic carbox- ylic acid containing at least eight carbon atoms or an ester or alkali metal or alkaline earth metal salt thereof; (C) ater; and (D) at least one organic solubilizing agent for component B.
  • A at least one of magnesium hydroxide, magnesium oxide, hy- drated magnesium oxide or a magnesium alkoxide
  • B at least one oleophilic organic reagent consisting essentially of an aliphatic cycloaliphatic or aromatic carbox- ylic acid containing at least eight carbon atoms or an ester or alkali metal or
  • the oil soluble magnesium products are added to the fuel in an amount sufficient to convert V 2 0 5 to magnesium orthova- nadate, Mg 3 V 2 0 8 , which melts at above 1100°C. Said temperature is below the typical gas turbine temperature when introducing the additive composition in the combustion chamber, but above the turbine gas inlet typical temperature due to the flame cooling process. Thus there will be no liquid V 2 0 5 that will act as a solvent for the alloy surface metal oxides and thus corrosion caused by V 2 0 5 is inhibited.
  • the first generation of oil soluble magnesium products had a concentration of magnesium as low as about 4%. The concentration was increased in the second generation up to about 14% magnesium and in the third generation the concentration could be raised further. However, there is a continued need for fuel additive compositions with still higher concentrations of magnesium or other metals capable of forming vanadates having a melting point above that of vanadium pentoxide .
  • the present invention is based on the discovery that crystalline particles of inorganic oxygen-containing metal compounds which when suddenly being subjected to high temperatures al- most "explosively" liberate a gaseous substance by evaporation, such as water vapour or carbon dioxide in case of e.g. magnesium hydroxide and magnesium carbonate, respectively, and are converted to particles of the corresponding metal oxide having a structure of increased porosity and reduced den- sity when compared to a corresponding oxide prepared by evaporation of gas at considerably lower temperatures.
  • This makes the oxide better suited for reaction with vanadium pentoxide will percolate easier into the more porous particles.
  • the said particle diameter less than 1-2 ⁇ m as a measurement of particle size is just a rough indicative measurement, as total mass, density, shape and porosity are important "size” properties to be considered as optimizing a fuel additive dispersion and its functional properties on ash melts and corrosion inhibition as well as deposit problems concerned.
  • the optimal "size” in all the size dimensions named will minimize deposit buildups due to the particles kinetic ad- sorption/desorption rate, preferably approaching 1,0 and thereby avoiding high adsorbing atomized and ⁇ 100 nm and avoiding high impaction rate into deposit by dense particles above the upper, >-1000 nm, micron sized limit.
  • a combination of at least one liquid selected from the group consisting of liquids soluble in oil on one hand and at least one dispersant selected from the group consisting of low molecular weight dis- persants and high molecular weight dispersants on the other is used as the dispersing system.
  • a fuel additive composition for the reduction/removal of vanadium-containing ash deposits in gas turbines and other by combustion of vanadium-containing fuel driven apparatuses which composition as its active ingredient comprises a compound of a metal capable of forming a va- nadate with vanadium of said ash deposits, which composition comprises
  • liquids soluble in oil dispersed in b) at least one liquid selected from the group consisting of liquids soluble in oil,
  • the premix to a treatment comprising size degradation and dispersant coating to a particle size distribution of the inorganic oxygen-containing metal compound and oxide essentially within the range of from 0.1 to 2 micron, pref- erably from 0.1 to 1 micron, under centrifugal or oscillation forces in the presence of a grinding medium and/or ultrasonic treatment until a plot of the sediment height in samples taken periodically during said treatment and centrifuged at a fixed rate for a fixed period versus time plateaus and the viscosity has decreased and come into a steady state.
  • an inorganic oxygen-containing compound of a metal selected from the group consisting of metals capable of forming vanadates having a melting point within the range of from 650°C to 2000°C with vanadium of ash deposits from vanadium-containing fuel, which inorganic oxygen-containing compound when heated up in a combustion flame liberates a gaseous substance by evaporation to form the corresponding oxide having a crystalline, porous low density structure, or the corresponding oxide obtained by heating the inorganic oxygen-containing compound at a temperature which is high enough to give the oxide in crystalline porous low density state but is below the melting point of the oxide, said inorganic oxygen-containing compound and said crystalline porous low density oxide having a particle size distribution essentially within the range of from 0.1 to 2 micron, preferably from 0.1 to 1 micron, as a component of fuel additive compositions for the reduction/removal of vanadium- containing ash deposits.
  • Vanadium-containing fuels are used within several fields of apparatuses driven by the combustion of fuel .
  • the corrosion problems caused by the presence of vanadium may be most serious in the case of gas turbines but such problems also exist in connection with e.g. boilers and diesel engines, wherein the metal temperatures are lower than in gas turbines and relatively less hazardous but still serious corrosion problems compared to gas turbines exist .
  • the metal of the inorganic oxygen-containing compound or oxide to be used in the invention should be chosen so that on reaction with the vanadium pentoxide a vanadate is formed that has a melting point exceeding the temperature at which the composition is used.
  • a metal should be chosen the melting point of the vanadate thereof preferably exceeds 1100°C.
  • such metals are magnesium the vanadate of which melts above 1100°C and yttrium the vanadate of which has a melting point above 1800°C, magnesium being the pre- ferred metal of these two metals for economical reasons.
  • vanadates having melting points enabling their use in the compositions according to the invention to be used in connection with apparatuses of lower temperature are among others, solely or in combinations, aluminum, zirconium, manganese, iron, copper, nickel and calcium. Often other metals than e.g. magnesium are either both rear and expensive or are environmental polluters, e.g. manganese etc.
  • the vanadates formed may be contaminated therewith resulting in a decrease or an increase of the melting point in comparison with 100% pure vanadate. Consideration should be paid thereto when selecting the metal compound or oxide used in the composition according to the present invention.
  • the active ingredient thereof comprising an inorganic oxygen-containing com- pound of a metal capable of forming a vanadate with vanadium of ash deposits is a hydroxide of said metal which hydroxide when heated up in a combustion flame is converted to the corresponding oxide having a crystalline porous low density structure .
  • hydroxides such as, for instance, magnesium hydroxide
  • hydroxides may be dehydrated almost “explosively" at very high temperatures (over 1000°C and below 2800°C) to form the corresponding metal oxide.
  • oxides formed by dehydration of hydroxides at lower temperatures such as just above the dehydration point of 350°C for the conversion of magnesium hydroxide to magnesium oxide
  • oxides formed at the higher temperatures are more porous and have a less dense crystalline structure than else.
  • said inorganic oxygen-containing compound of a metal capable of forming a vanadate with vanadium of ash deposits is a metal carbonate.
  • the carbonate When suddenly being heated at high temperatures such as in a combustion flame the carbonate will liberate carbon dioxide and form the corresponding metal oxide having a crystalline porous low density structure analogously to the formation of the oxide from an hydroxide at very high temperatures .
  • said compound of a metal capable of forming a vanadate with vanadium of ash deposits is a metal oxide having a crystalline porous low den- sity structure.
  • Such oxides may, for instance, be prepared from the corresponding hydroxides or carbonates by heating at a high temperature.
  • the conversion of the hydroxide or carbonate should be carried out below the point at which the oxide tends to increase in density, but close thereto and far below it starts melting. Above said point at which the oxide "tends to start melting” the pore structure continually decreases as approaching the critical melting point, at which maximum density will be reached, for e.g. magnesium oxide at 2750°C.
  • Such a heat treatment to achieve minimum porous density oxide may be performed by passing a dry powder of an optimal size distribution of the hydroxide or carbonate through a flame having a temperature suitably adapted below the density decreasing point of the oxide as indicated above.
  • low density metal oxides may also be prepared by suddenly subjecting submicron sized crystals of an inorganic oxygen-containing metal compound, preferably a hydroxide or a carbonate, which when heated to a high temperature liberates a gaseous substance by evaporation, to heating at an appropriately high temperature in an oven.
  • an inorganic oxygen-containing metal compound preferably a hydroxide or a carbonate
  • the present inventors rapidly heated sub-micron sized particles of magnesium hydroxide in an oven at a temperature of 1000°C for a short time which resulted in the conversion of the magnesium hydroxide into magnesium oxide having a density of ⁇ 1.4 g/cm 3 .
  • Similar heating of magnesium carbonate in an oven at a temperature of 1300°C resulted in magnesium oxide having a density as low as 1.03 g/cm 3
  • the low density metal oxide should preferably have a density of at most 2.0 g/cm 3 , more preferably below 1.5 g/cm 3 and most preferably below 1.0 g/cm 3 .
  • the inorganic oxygen-containing metal compounds and porous low density metal oxides incorporated in the fuel additive composition according to the invention should have a particle size distribution essentially within the range of from 0.1 to 2 micron, preferably from 0.1 to 1 micron, preferably narrowly distributed close to the optimal size within that range of 0.1 to 1 micron.
  • said compounds and oxides should have a particle size optimal distribution which is adapted to be most effective at the temperature at which a solid, porous metal vanadate is formed and to form ash particles which deposit as little as possible [due to thermody- namic surface adsorption and desorption properties of the particles] and form as loose a deposit as possible [due to the porosity of the particles and thereby the epitactic and topotactic deposits lattice build-up structure] .
  • the particle size distribution should be selected so that the metal vanadates formed in the flame are not given sufficient time to melt before reaching areas of the apparatus having a temperature below the melting point of the vanadates.
  • the porous oxides added to the fuel are not delayed in their re- action to the formation of the vanadates in the heat zone compared to the porous oxides formed from, for instance hydroxides or carbonates bypassing the heat zone.
  • a hydroxide or a carbonate should be used which has a particle size which is greater than that of the same hydroxide or carbonate to be used in apparatuses operating at a lower heat zone flame tern- perature.
  • surface enlarged porous metal oxides should be used at temperatures lower than those prevailing in gas turbine heat zones, i.e. they may preferably be used in boilers and diesel engines if an extraordinarily low operating temperature in the heat zone would be a disadvantage of the addition of the heat zone by passing metal hydroxide into the fuel .
  • the size of the oxide particles is in the range not below 0.1 micron and not above high density impacting 2 micron, preferably exhibiting a particle size distribution injected into the fuel around 0.4 to 0.5 micron, in order to reduce the deposit accumulation due to the Brown Movement Kinetic affecting the particles surface adsorption and desorption rate on the deposit surface and that the said particles have a surface area including internal pores surface interface area comparable to that of crystalline high density oxide particles of a particle size far below 0.1 ⁇ m to maximize the reactive surface.
  • Such a high surface area will solely be achievable by porous particles.
  • the inventors have noted that dehydration or evaporation of magnesium hydroxide particles at high temperature causes a split size reduction and volume expansion and agglomeration into a less tight particle size distribution depending on the particles individual initial size. For this reason the particle size of the particles used in the fuel additive compositions according to the invention will generally be distributed in a somewhat enlarged size range below and above when using the hydroxide in comparison with the use of a size tai- lored oxide .
  • the particles of the inorganic oxygen-containing compound as well as the oxide particles should preferably have a narrow (low variance) particle size distribution, preferably around a cross section largest distance arithmetic mean in the 0.2 to 0.5 micron range and with a variance for a lognormal distribution in the range ⁇ 0.2 ⁇ ⁇ ⁇ ⁇ 0,6.
  • the inorganic oxygen-containing metal compound or oxide particles are dispersed in at least one liquid selected from the group consisting of liquids soluble in oil.
  • Contemplated for use in the fuel additive composition accord- ing to the invention are liquids selected from the group consisting of mineral oils, synthetic oils, highly aromatic naphtha, diesel oil, vegetable oils, esterified vegetable oils, animal oils and esterified animal oils.
  • vegetable oils and esters thereof to be used in the fuel additive compositions according to the invention include, but are not limited to, peanut oil, coconut oil, corn oil, linseed oil, rape-oil, palm oil, sunflower oil, olive oil, tall oil and esters thereof, the preferred representa- tive thereof being rape-oil methyl ester (RME) .
  • RME rape-oil methyl ester
  • animal oils to be used in the fuel additive compositions according to the invention include, but are not limited to, fish liver oil, train-oil and liquid modified fat from slaughter-houses.
  • the preferred representatives of the liquids soluble in oil to be used in the present invention are diesel oil and rape- oil methyl ester.
  • the inorganic oxygen- containing metal compound particles or metal oxide particles have become dispersed in at least one liquid which, as stated above, is selected from the group consisting of liquids soluble in oil by means of at least one dispersant selected from the group consisting of low molecular weight dispersants and high molecular weight dispersants.
  • low molecular weight dispersants as used here and in the claims is used to designate dispersants having a molecular weight usually within the range of from 1.000 to 2.000g/mole.
  • dispersants may be classified to manifold properties as described below.
  • high molecular weight dispersants as used here and in the claims is used to designate dispersants having a molecular weight usually within the range of from 5,000 to 30.000 g/mole.
  • the conventional low molecular weight dispersants are categorized according to their structure as anionic, cationic, amphoteric and nonionic. Their efficiency is de- fined by a) absorption of polar groups to the surface of the particles to be dispersed and b) the behavior of a non-polar chain of the medium surrounding the particle.
  • a colloid is a liquid droplet or a solid particle in the size range of at most 1-2 ⁇ m but normally submicron or in the range of one molecule to many molecules forming a size of 2 -999 nm in average diameter.
  • Steric dispersants adsorb and coat the particle surfaces.
  • a surface is an interface between two non- soluable compounds, one liquid and one solid state or two liquid states.
  • colloid dispersion is a true dispersion formed of particles and such dispersions is commonly defined as a micelle dispersion.
  • a huge group of steric dis- persants forms micelles both in oil and water systems.
  • steric dispersants form micelles in a selected oil soluble solvent, when the hydrophobic tail penetrates into the solvent.
  • the stability of such dispersions is depending on many different forces defining the stability boundaries for the other unit tail.
  • the other said molecular hydrophilic tail adsorbs to the particle surface and will be bondable to the surface of the particle in many different ways due to the kind of (1) anchor groups, (2) the number of repeating units in the polymer and (3) if the dispersant is a homo polymers dispersants whereas the repeating units are of one kind or is a co-polymer of two different kinds and (4) the electrostatic properties.
  • the known art of the described colloid dispersion systems admits a suitable tool to tailor a stable composition of solid particles suitable as a fuel additive.
  • magnesium carboxylates and magnesium sul- fonates has been widely used to create stable metal oxide dispersions in fuel additives.
  • the kind of dispersants suitable is enlarged to admit higher concentrations of stable solid dispersions.
  • Hypermer ® LP4 a ine derivate of a fatty acid condensation polymer from UNIQEMA, Everberg, Belgium
  • EFKA 4010 modified polyurethane, from EFKA Inc., Heerenveen, the Netherlands
  • Rhodafac ® RE 610 nonylphenol ethoxylate based phosphate esters, from Rhodia Inc, France
  • dispersant layer that coats the particles has to be thin. This is achieved by a small low molecular weight dispersant as characterized by Rhodafac ® RE 610 having two tail units penetrating into the solvent or Hypermer ® LP4. When the volume of solvent in the composition increases and the particle concentration is lower it is suitable instead to choose a high molecular weight dispersant for instance EFKA 4010.
  • High molecular weight dispersants have pendent anchoring groups, which adsorb to the surface of the particles to be dispersed. Their mechanism of action is by hydrogen bonding, dipole-dipole interactions or Van der Waal forces.
  • the polymeric framework is sufficiently great to give an effect called sterical stabilization.
  • the preferred dispersants to be used in the present invention are anionic and amphoteric low molecular weight dispersants.
  • anionic low molecular weight dispersants to be used in the present invention include magnesium soaps of carbox- ylic and sulfonic acids.
  • Such dispersants and comparable dispersants containing magnesium are not preferable, as they may comprise atom sizes magnesium that depart from the scope of porous oxides feature, as a partial or total disadvantage to the aimed invention.
  • the fuel additive composition according to the present invention will generally comprise the submicron or nano-sized inorganic oxygen-containing metal compound or oxide (component a) ) in a concentration of from 10 to 65% by volume, preferably from 20 to 50% by volume and more preferably from 30 to 50% by volume, and most preferably from 40 to 50% by volume, calculated on the total volume of the compositions, the balance to 100% by volume essentially consisting of components b) and c) and possibly a minor amount of water (generally less than 0.5% by volume) such as moisture emanating e.g. from the use of not fully dry starting materials, such as the hygroscopic substance magnesium hydroxide or deliberately added to regulate the viscosity and stability of the composition.
  • component a) inorganic oxygen-containing metal compound or oxide
  • the upper limit of the concentration of inorganic oxygen- containing compound or oxide in each specific case is defined by the particle volume size and specific dispersants depletion limit due to the specific particle size that may destabilize the dispersion.
  • the upper limit will increase with increasing average particle size.
  • the upper limit will be around 50% by volume in case of particles having a particle size low variance distribution, as a distribution having variance from ⁇ 0.2 to ⁇ 0 . 6 for the log- normal distribution around a mean size from 500 to 200 nano- meters (nm) respectively
  • the volume ratio component b) to component c) generally depends on the specific substances used as those components and the amount of particles to be dispersed. The optimum ratio in each specific system may easily be determined in a series of experiments varying said ratio for which experiments no inventive activity should be required.
  • the fuel additive composition according to the invention is prepared according to said another aspect of the invention by means of the process according to the invention, which process comprises
  • the premix to a treatment comprising size degradation and dispersant coating to a particle size distribution of the inorganic oxygen-containing metal compound and oxide essentially within the range of from 0.1 to 2 micron, pref- erably from 0.1 to 1 micron, under centrifugal or oscillation forces in the presence of a grinding medium and/or ultrasonic treatment until a plot of the sediment height in samples taken periodically during said treatment and centrifuged at a fixed rate for a fixed period versus time plateaus and the viscosity has decreased and come into a steady state.
  • Metal compound particles to be used in the process according to the present invention should not contain crystal -water and have a low moisture content, if necessary obtained by a dry- ing process, preferably a moisture content far below 0.5% by weight .
  • the particle size of the metal compound or oxide particles should not be exceedingly greater than the size of the particles of composition prepared by means of the process and generally particle sizes within the submicron range should be used, but small particles of a substantial amount below 0,1 microns easily adsorbing the deposit areas and having a low desorbtions rate should be avoided.
  • the particles of the metal compound or oxide are added to a vessel containing a mixture of said at least one liquid selected from the group consisting of liquids soluble in oil and at least part of said at least one dispersant under mixing to form a premix allowing the tennperature to rise during the mixing, e.g. to a temperature within the range of from 50°C to the upper limit ⁇ 85°C defined by the centrifugal forces and the viscosity to avoid cavitation of the grinding media in order to reduce the viscosity of the premix.
  • a basket mill is used for the procedure of the second step of the process according to the present invention.
  • Such mills are available on the market and are, for instance, sold in different models under the trade name Turbomill by Mirodur SpA, Aprilia, Italy.
  • the grinding media used are e.g. small zirconium balls, the diameter of which is chosen in accordance with the intended particle size of the metal compound and oxide particles, re- spectively, after grinding so that said diameter is increased when larger particles are wanted. Generally said diameter will be within the range of from 0.8 to 1.2 mm, however, balls of uniform size being used in each specific case. Balls of other materials known as suited for use as grinding media, e.g. steel and glass, can also be used in the process according to the invention.
  • a zirconium ball size of 0.8 mm is, for instance, sufficient to reach the desired size for e.g. Mg (OH) 2 -particles and efficiently disperse the particles in accordance with the invention.
  • the premix mentioned above is filled into the basket mill vessel and rotating is started and speeded up to full power loading allowing temperature to rise to about 75-85°C. All moisture that evaporates during the basket mill operation should be evacuated from the vessel .
  • Samples are taken at intervals of 30 to 70 minutes such as 1 hour and centrifuged at a fixed rate, e.g. within the range of from 2000 rpm to 4000 rpm, such as 3000 rpm, for a fixed period within a range of from e.g. 30 minutes to 1 hour, such as 45 or 50 minutes, and the height of the sediment of each sample measured.
  • a fixed rate e.g. within the range of from 2000 rpm to 4000 rpm, such as 3000 rpm
  • a fixed period within a range of from e.g. 30 minutes to 1 hour, such as 45 or 50 minutes
  • grinding may be performed by means of oscillation buckets.
  • grinding ultrasonic treatment may be applied.
  • the design of grinding mills commonly supplied has to be ad- justed for the engine effect upwards to achieve at least an accelerative force above 50 g on the liquid to reach the limit force needed to override the tensions to disaggregate the present smallest nano particles.
  • Preferably 70 g is needed as desired to economically optimize the capacity dis- persed per kWh etc.
  • the liquid lubricant film must hold the balls of e.g. a basket mill apart from each other. Otherwise the cavitating balls will degrade themselves rapidly. There is no possibility to achieve static pressure to degrade agglomerates and grind nano-scaled particles.
  • the force here transmitted, to achieve degradation has to be transmitted to the electromag- netic interference between particle surfaces and the intermediate liquid.
  • a media mill optimizing the following parameters preferably achieves this.
  • Ball density Ball volume relative to inlet power to be transmitted. 6. Accelerative force in g-number (Af)
  • the acceleration force is proportional to the radius for a body motion in a circular orbit and proportional to the square power for the angular velocity.
  • Equation (2) Square root of (Af*9.82*/r) divided by (2*7T*60)
  • An acceleration force (Af) of 70g is preferable to exceed the tensions in the crystal aggregate.
  • equation (2) tells us the orbit frequency for different kind of mills and other kinds of power transmission facilities.
  • a certain limit e.g. 10 mm we cannot apply the power by centripetal force as in a basket mill of understandable reasons. Instead an high frequency oscillatory or vibrato vessel is preferable.
  • a 210 mm radius basket needs a rotating speed of 546 rpm to achieve a peripheral force of
  • a small body in 10 mm radius oscillatory vessel needs a rotation speed of 3541 rpm or 59 Hertz.
  • ultrasonic methods may be used, as dispersion par se is desired. Similar to the oscillatory vessel case equation (2) will help us to define the frequency for different ultrasonic amplitudes or wavelengths to be applied. As a conventional ultrasonic frequency is 20-40 kHz for e.g. 35 kHz the desired amplitude is 15 nm, but a substantially higher amplitude in the range above 1-10 microns is a necessity due to achieve sheer beams for the entire particles and not only for a small limit part on a particles surface area. The amplitude has to substantially exceed the particles size to admit surface coating and particles to cavitate. Thereby, ultrasonic equipment is also contemplated for use in the pre- sent invention, especially as increased power density is needed to achieve efficient fast coating on the small part of the very small nano particles to get a fully stable dispersion not reaggregating.
  • the magnesium hydroxide used was Ankermag ® -HH from Magnifin Magnesia facility GmbH, Austria.
  • the magnesium powder contains > 98.0 % by weight (wt%) Mg(OH) 2 and ⁇ 0.5 wt% water.
  • Specific surface 9-12 m 2 /g equivalence a mean size for a dense sphere diameter range from 200-260nm or in fact the largest diameter of the thin flakes crystals average ⁇ 500nm.
  • the crystals D50 diameter is -900 nm, i.e. the median size diameters in the distribution.
  • the crystal agglomerate upper limit diameter is less than approximately 50 microns.
  • the preparation process according to the invention admits feeding by much larger particles, preferably a surface area above > 3-4 m/g.
  • the dispersant used was Rhodafac ® RE 610, from Rhodia Inc, France, which is characterized by the manufacturer as nonyl- phenol ethoxylate based phosphate esters .
  • Rape-oil methyl ester was supplied by Svenska Ekobranslen AB, Sweden.
  • Rhodafac ® RE610 and 270 kg of rape-oil methyl ester (RME) having a moisture content of ⁇ 0.05% by weight were mixed in a dissolver vessel (Disolver DTM49 from Westerlins Maskinfabrik AB, Malm ⁇ , Sweden) to a homogenous mixture.
  • a dissolver vessel Disolver DTM49 from Westerlins Maskinfabrik AB, Malm ⁇ , Sweden
  • the premix was then transferred to the vessel of a basket mill (Turbomill ® 2, from Mirodur SpA, Aprilia, Italy, with an engine effect of 55kW) containing balls of zirconium having a diameter of 0.8 mm as the grinding medium and rotation of the basket was started and speeded up to full power loading.
  • a basket mill Trobomill ® 2, from Mirodur SpA, Aprilia, Italy, with an engine effect of 55kW
  • the temperature was allowed to increase to 75°C-85°C, i.e. securely below the upper limit where the reduced viscosity achieved by the increase in temperature will allow the balls of the milling medium to touch each other by chance.
  • the temperature was kept stable until the samples taken at intervals of 1 hour and centrifuged at a rate of 3000 rpm for 50 minutes indicated a rapid decrease in the height of the pellet obtained by such centrifugation after approximately 4- 6 hours, due to operation temperature and the applied centrifugal force.
  • the basket mill was kept running until the premix was fully dispersed which occurred as decreasing the rotation in accordance to the decrease in the height of the pellet obtained by centrifuging samples as above until approaching a steady state. Then additional 20 kg of Rhodafac ® RE610 and 20 kg of rape-oil methyl ester (in addition, if desired 1-5 liter water may be added per ton to achieve increased stabilization of the particles) were added and the grinding process continued for approximately 15 minutes.
  • the completed process was shut down and the composition liquid was pumped into barrels and samples were collected. If desired for the specific applications the liquid composition is diluted by RME before barreling it up.
  • the Mg content by ash test was -29% by weight and the Mg(OH) 2 content was 69% by weight (-46% by volume) and the upper tail of the size distribution was below 1,0 micron and the main particle flakes shown by a standard scanning electronmicro- scope were in the range 0.2-0.5 micron.
  • the premix was then transferred to the vessel of a basket mill (Turbomill ® 2, from Mirodur SpA, Aprilia, Italy, with an engine effect of 55kW) containing balls of zirconium having a diameter of 0.8 mm as the grinding medium and rotation of the basket was started and speeded up to full power loading.
  • the temperature was allowed to increase to 75°C-85°C, i.e. securely below the upper limit where the reduced viscosity achieved by the increase in temperature will allow the balls of the milling medium to touch each other by chance.
  • the temperature was kept stable until the samples taken at intervals of 1 hour and centrifuged at a rate of 3000 rpm for 50 minutes indicated a rapid decrease in the height of the pellet obtained by such centrifugation after approximately 4- 6 hours, due to operation temperature and the applied g- force.
  • the basket mill was kept running until the premix was fully dispersed which occurred as decreasing the rotation in accordance to the decrease in the height of the pellet obtained by centrifuging samples as above until approaching a steady state. Then additional 40 kg of Rhodafac ® RE610 (in addition, if desired 1-5 liter water may be added per ton to achieve increased stabilization of the particles) were added and the grinding process continued for approximately 15 minutes .
  • the completed process was shut down and the composition liquid was pumped into barrels and samples were colleted. If desired for the specific applications the liquid composition is diluted by dieseloil before barreling it up.
  • the Mg content by ash test was -29% by weight and the Mg(OH) 2 content was 69% by weight (-46% by volume) and the size distribution of the upper tail was below 1,0 micron and the main particle flakes shown by a standard scanning electronmicro- scope were in the range 0.2-0.5 micron.
  • the specific surface area for Mg (OH) 2 and MgO was measured by Multipoint Surface Area N 2 -gas at 77° Kelvin adsorption isotherm and pore distribution.
  • the pore diameter at surface had its distinct high frequency with as micropores within the range 3.5-6.5 nm for the almost fully dense Mg(OH) 2 and for the converted low density MgO as mesopores within the range of 10-60 nm with the mode-frequency just below 30 nm
  • MgO has a solely crystalline lattice structure whereby the crystals are not to any degree an amorphous unordered structured crystal .
  • the expanded and to some extent sintered crystals contain open pores through the crystal surface as well as closed pores within the crystals due to the low density and the small 20% increase in specific surface area as loosen 3/5 atoms out of the crystal volume.
  • magnesium carbonate was rapidly heated in an oven at a temperature of 1300°C and the density of the magnesium oxide thus formed was measured by a pyknometer and found to be 1,03 g/cm 3
  • a fuel additive composition according to the present invention was used in a large-scale comparative test in a power plant, wherein two comparable 120 MW gas turbines were applied in parallel, both being fed with the same fuel until injecting the composition according to the invention and a prior art composition (KL 200 from Baker Petrolite, USA) , one for each gas turbine with the same present common pumps into the oil flow on its final short way into the combustion cham- ber.
  • the gas turbines were completely up kept at onset including new turbine blades.
  • the fuel additive composition according to the invention used in this experiment had a density of -1.56 g/cm 3 and contained ⁇ 69 % by weight of magnesium hydroxide particles and thereby 29% Mg by weight having a particles size distribution around mean -300-500 nm with a variance mean for the lognormal distribution of -0.4 and 4% by weight of Rhodafac ® RE610 from Rhodia Inc, France and 27% by weight of REM.
  • KL 200 is a magnesium oxide over-based magnesium carboxylate vanadium inhibitor with a density of 1.22 g/cm 3 containing 20% Mg as specified by the supplier.
  • the wash cycle is the time range from start of operation until the gas turbine needs to be cleaned up for deposits due to technical and economical disadvantages from the accumu- lated deposits of ash compounds.
  • the volume of the pores in the deposits was estimated before auto wash. By letting a liquid be absorbed into deposit pieces it was found that deposits in accordance with the invention were substantially more porous in the range of an ad- ditional pore volume for deposit comparable locations of 30- 115% and in accordance with that a decreased density in the rage up to 25% was reported. In addition the liquid absorb- ance speed was much faster for the deposits in accordance with the invention.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

L'invention concerne une composition d'additif de combustible utilisée pour réduire/éliminer des dépôts de cendres contenant du vanadium, dans des turbines à gaz et autres, par combustion de dispositifs actionnés par du combustible contenant du vanadium. Ladite composition comprend comme principe actif, un composé d'un métal apte à former un vanadate avec le vanadium desdits dépôts de cendres. Ladite composition comprend : a) comme composé de métal apte à former un vanadate avec le vanadium desdits dépôts de centres a1) un composé inorganique contenant de l'oxygène, dudit métal sous forme particulaire, ledit composé contenant de l'oxygène libérant une substance gazeuse par évaporation, lorsqu'il est chauffé dans une flamme de combustion, et forme l'oxyde de métal correspondant qui présente une structure cristalline poreuse de masse volumique réduite ou a2) ledit oxyde de métal présentant une structure cristalline poreuse de masse volumique réduite, ledit composé inorganique contenant de l'oxygène a1) et ledit oxyde de métal correspondant a2) ayant une répartition granulométrique se situant principalement entre 0,1 et 2 microns, de préférence entre 0,1 et 1 micron et ledit oxyde de métal correspondant a) ayant une masse volumétrique d'au plus 2,0 g/cm3, en dispersion dans b) au moins un liquide sélectionné dans le groupe comprenant des liquides solubles dans l'huile, à l'aide c) d'au moins un dispersant sélectionné dans le groupe comprenant des dispersants de faible poids moléculaire et des dispersants de poids moléculaire élevé. L'invention concerne également un procédé de production de ladite composition, qui comprend le fait de mélanger une poudre du composant a) défini ci-dessus dans un mélange de composants b) et c) afin de former un mélange préalable qui est ensuite soumis à une fragmentation et à un revêtement par dispersant sous l'effet de forces centrifuges ou de forces oscillantes et/ou à un traitement ultrasonore pour parvenir à la répartition granulométrique mentionnée précédemment.
PCT/SE2003/001446 2002-09-17 2003-09-16 Composition d'additif de combustible et sa preparation WO2004026996A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP03797773A EP1543094A1 (fr) 2002-09-17 2003-09-16 Composition d'additif de combustible et sa preparation
AU2003261053A AU2003261053A1 (en) 2002-09-17 2003-09-16 Fuel additive composition and its preparation
EA200500499A EA010070B1 (ru) 2002-09-17 2003-09-16 Композиция присадки к топливу и ее получение
US10/528,079 US20060059768A1 (en) 2002-09-17 2003-09-16 Fuel additive composition and its preparation
CA002498151A CA2498151A1 (fr) 2002-09-17 2003-09-16 Composition d'additif de combustible et sa preparation

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0202760A SE0202760D0 (sv) 2002-09-17 2002-09-17 Fuel additive composition and its preparation
SE0202760-5 2002-09-17

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WO2004026996A1 true WO2004026996A1 (fr) 2004-04-01

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EP (1) EP1543094A1 (fr)
CN (1) CN100443573C (fr)
AU (1) AU2003261053A1 (fr)
CA (1) CA2498151A1 (fr)
EA (1) EA010070B1 (fr)
SE (1) SE0202760D0 (fr)
WO (1) WO2004026996A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097952A1 (fr) * 2004-03-31 2005-10-20 The Lubrizol Corporation Dispersions a forte teneur en matieres solides
WO2007120262A2 (fr) * 2005-11-10 2007-10-25 The Lubrizol Corporation Procédé de contrôle de sous-produits ou de polluants de la combustion de carburants/combustibles
US8460404B2 (en) 2008-05-15 2013-06-11 The Lubrizol Corporation Quaternary salts for use as surfactants in dispersions
WO2016162718A1 (fr) * 2015-04-10 2016-10-13 Ge Energy Products France Snc Procédé de fonctionnement d'une turbine à gaz avec injection d'yttrium et/ou de magnésium
WO2017096334A1 (fr) * 2015-12-03 2017-06-08 General Electric Company Inhibiteurs de corrosion du vanadium à base d'yttrium et de magnésium
FR3044684A1 (fr) * 2015-12-03 2017-06-09 Ge Energy Products France Snc Inhibiteurs de la corrosion vanadique a base d'yttrium et de magnesium
WO2018002690A1 (fr) 2016-06-29 2018-01-04 Cemex Research Group Ag Procédé pour réduire les dépôts, les croûtes et la formation d'anneaux dans la production de clinker
EP3438326A1 (fr) * 2017-08-01 2019-02-06 General Electric Company Systèmes et procédés pour inhibiteurs de la corrosion vanadique
US10513665B2 (en) 2016-04-19 2019-12-24 Saudi Arabian Oil Company Vanadium corrosion inhibitors in gas turbine applications

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EA012177B1 (ru) * 2004-07-02 2009-08-28 Монсанто С.А.С. Новая композиция биотоплива
ITMI20072292A1 (it) * 2007-12-06 2009-06-07 Itea Spa Processo di combustione
ITMI20072291A1 (it) * 2007-12-06 2009-06-07 Itea Spa Processo di combustione
ITMI20072290A1 (it) * 2007-12-06 2009-06-07 Itea Spa Processo di combustione
US10557099B2 (en) 2017-08-09 2020-02-11 General Electric Company Oil based product for treating vanadium rich oils
US10577553B2 (en) * 2017-08-09 2020-03-03 General Electric Company Water based product for treating vanadium rich oils
CN113511694B (zh) * 2021-05-21 2022-12-27 南京乐透思高新材料科技有限公司 一种复合海绵材料及其制备方法和在处理高盐、高热值废水中的应用

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US2781005A (en) * 1950-06-28 1957-02-12 Power Jets Res & Dev Ltd Method of reducing vanadium corrosion in gas turbines
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US3692503A (en) 1969-02-26 1972-09-19 Apollo Chem Activated manganese containing additive for fuels
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005097952A1 (fr) * 2004-03-31 2005-10-20 The Lubrizol Corporation Dispersions a forte teneur en matieres solides
AU2005230823B2 (en) * 2004-03-31 2010-09-16 The Lubrizol Corporation High solids content dispersions
EP2261310A2 (fr) 2004-03-31 2010-12-15 The Lubrizol Corporation Dispersions à teneur élevée en solides et compositions de graisses les contenant
US8123823B2 (en) 2004-03-31 2012-02-28 The Lurbizol Corporation High solids content dispersions
WO2007120262A2 (fr) * 2005-11-10 2007-10-25 The Lubrizol Corporation Procédé de contrôle de sous-produits ou de polluants de la combustion de carburants/combustibles
WO2007120262A3 (fr) * 2005-11-10 2008-04-03 Lubrizol Corp Procédé de contrôle de sous-produits ou de polluants de la combustion de carburants/combustibles
US8460404B2 (en) 2008-05-15 2013-06-11 The Lubrizol Corporation Quaternary salts for use as surfactants in dispersions
WO2016162718A1 (fr) * 2015-04-10 2016-10-13 Ge Energy Products France Snc Procédé de fonctionnement d'une turbine à gaz avec injection d'yttrium et/ou de magnésium
WO2017096334A1 (fr) * 2015-12-03 2017-06-08 General Electric Company Inhibiteurs de corrosion du vanadium à base d'yttrium et de magnésium
FR3044684A1 (fr) * 2015-12-03 2017-06-09 Ge Energy Products France Snc Inhibiteurs de la corrosion vanadique a base d'yttrium et de magnesium
US10184091B2 (en) 2015-12-03 2019-01-22 General Electric Company Yttrium and magnesium based vanadium corrosion inhibitors
US10513665B2 (en) 2016-04-19 2019-12-24 Saudi Arabian Oil Company Vanadium corrosion inhibitors in gas turbine applications
WO2018002690A1 (fr) 2016-06-29 2018-01-04 Cemex Research Group Ag Procédé pour réduire les dépôts, les croûtes et la formation d'anneaux dans la production de clinker
EP3438326A1 (fr) * 2017-08-01 2019-02-06 General Electric Company Systèmes et procédés pour inhibiteurs de la corrosion vanadique
US10907547B2 (en) 2017-08-01 2021-02-02 General Electric Company Systems and methods for vanadium corrosion inhibitors

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CN1681907A (zh) 2005-10-12
CA2498151A1 (fr) 2004-04-01
AU2003261053A1 (en) 2004-04-08
EA010070B1 (ru) 2008-06-30
US20060059768A1 (en) 2006-03-23
SE0202760D0 (sv) 2002-09-17
EA200500499A1 (ru) 2005-08-25
CN100443573C (zh) 2008-12-17
EP1543094A1 (fr) 2005-06-22

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