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WO2017096334A1 - Inhibiteurs de corrosion du vanadium à base d'yttrium et de magnésium - Google Patents

Inhibiteurs de corrosion du vanadium à base d'yttrium et de magnésium Download PDF

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Publication number
WO2017096334A1
WO2017096334A1 PCT/US2016/064870 US2016064870W WO2017096334A1 WO 2017096334 A1 WO2017096334 A1 WO 2017096334A1 US 2016064870 W US2016064870 W US 2016064870W WO 2017096334 A1 WO2017096334 A1 WO 2017096334A1
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WIPO (PCT)
Prior art keywords
yttrium
magnesium
vanadium
thermal equipment
corrosion inhibitors
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2016/064870
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English (en)
Inventor
Pierre Olivier MONTAGNE
Sundar Amancherla
Krishnamurthy Anand
David Terry TRAYHAN, Jr.
Matthieu Paul Frederic VIERLING
Maher Aboujaib
Abdurrahman Abdallah KHALIDI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
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Filing date
Publication date
Priority claimed from FR1561782A external-priority patent/FR3044684B1/fr
Application filed by General Electric Co filed Critical General Electric Co
Publication of WO2017096334A1 publication Critical patent/WO2017096334A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/12—Inorganic compounds
    • C10L1/1266—Inorganic compounds nitrogen containing compounds, (e.g. NH3)
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/30—Organic compounds compounds not mentioned before (complexes)
    • C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/185—Refractory metal-containing compounds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
    • F01D25/002—Cleaning of turbomachines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D25/00—Component parts, details, or accessories, not provided for in, or of interest apart from, other groups
    • F01D25/007—Preventing corrosion

Definitions

  • the subject matter disclosed herein relates generally to thermal equipment, and more particularly to inhibition of high temperature corrosion thereof.
  • Thermal equipment such as boilers, diesel engines, gas turbines, furnaces, and process reactors may be used to burn certain liquid fuels.
  • the fuels may contain traces of metallic contaminants such as vanadium, sodium, potassium, calcium, and lead that need to be treated prior to their combustion in order to attenuate the high temperature corrosion effects of these metals on thermal equipment.
  • the metallic salts contained in the fuels are water soluble and may be extracted upstream of the thermal equipment. For example, fuel washing operations with water, followed by water/fuel separation with the aid of electrostatic separators or centrifuges, are commonly implemented to separate water soluble metallic salts such as chlorides and sulfates of sodium, potassium and partially calcium.
  • the vanadium derivatives contained in the fuels are organic in nature and are not water soluble and therefore cannot be extracted by such a washing operation.
  • the presence of such organic compounds of vanadium in liquid fuels burned in the thermal equipment is likely to cause high temperature corrosion of the metallic materials in contact with the combustion gases.
  • a process for inhibiting vanadium corrosion in thermal equipment includes introducing vanadium corrosion inhibitors into the thermal equipment.
  • the vanadium corrosion occurs in high temperature parts of the thermal equipment that burns a fuel containing vanadium, such that vanadium pentoxide (V2O5) is formed during combustion of the fuel.
  • the vanadium corrosion inhibitors include an yttrium-based inhibitor comprising yttrium oxide (Y2O3) and a magnesium-based inhibitor comprising magnesium oxide (MgO).
  • a process includes inhibiting vanadium corrosion in thermal equipment by conversion of vanadium pentoxide (V2O5) into other chemical species using vanadium corrosion inhibitors, the V2O5 being formed during combustion of a vanadium-containing fuel in the thermal equipment.
  • the vanadium corrosion inhibitors inhibit vanadium corrosion by reducing an amount of V2O5 according to a reaction: V2O5 + y Y2O3 + m (1 - y) MgO - 2y YVO4 + (1 - y) Mg3V208 + (1 - y) (m - 3) MgO, wherein y is between about 0.05 to 0.95, and m is between about 3 to 15.
  • a process includes inhibiting vanadium corrosion in thermal equipment using vanadium corrosion inhibitors, the thermal equipment being used to burn vanadium-containing fuels.
  • the vanadium corrosion inhibitors include an yttrium-based and a magnesium-based vanadium corrosion inhibitor.
  • the inhibiting of the vanadium corrosion is performed such that vanadium pentoxide (V2O5), vanadium oxide, and yttrium sulfate are not released from the thermal equipment.
  • FIG. 1 is a plot illustrating a comparison between different turbine performance levels as a function of time, in accordance with certain embodiments of the disclosure.
  • Embodiments of the present invention concern the inhibition of high temperature corrosion of materials of thermal equipment such as boilers, diesel engines, gas turbines, furnaces and process reactors, which, in their furnace, burn vanadium-contaminated fuels.
  • the "flame temperature” of a gas turbine which largely determines its efficiency, is the temperature that prevails at the inlet of the turboexpander and not that which is present in the flames, which exceeds 2000 °C on the flame front.
  • the metallic salts contained in the fuels can, when they are water soluble, be extracted upstream of the thermal equipment; this is how "fuel washing" operations with water, followed by water/fuel separation with the aid of electrostatic separators or centrifuges, are commonly implemented to separate water soluble metallic salts such as chlorides and sulfates of sodium, potassium and partially calcium.
  • the vanadium derivatives contained in the fuels are organic in nature and have as major drawback that they are not water soluble but fat soluble and therefore cannot be extracted by such a washing operation.
  • the presence of such organic compounds of vanadium in liquid fuels burned in thermal equipment is likely to cause high temperature corrosion of the metallic materials in contact with the combustion gases.
  • the vanadium reacts with oxygen to form one of the oxides VO, V2O3, V2O4 (or VO2) or V2O5: whereas the first three oxides are refractory, with melting points in excess of 1500°C, vanadium pentoxide V2O5, which is formed in the highly oxidizing flames in gas turbines in particular, melts at a temperature of 670°C.
  • This oxide is therefore present in liquid form in the operating conditions of the turbine and the fraction that is deposited on the surfaces of the hot parts may thereby cause electrochemical type corrosion in a molten salt environment.
  • V2O5 vanadium pentoxide V2O5
  • inhibitors The classical representatives of these inhibitors are alkaline earth compounds such as calcium oxide, when the fuel does not contain sulfur, or magnesium salts, which can be applied in water soluble or fat soluble form.
  • Such magnesium-based inhibitor additives once introduced into a flame, decompose there into magnesium oxide (MgO), which reacts with V2O5 to form magnesium vanadate.
  • a sufficient quantity of magnesium is introduced to generate magnesium orthovanadate, formula Mg3V20s, whose high melting point (1070°C) allows the vanadium charged particles to pass through the "hot gas path" of the turbine in solid form without causing corrosion of the hot parts of the said turbine.
  • the inhibitor dosage must be sufficient to both allow all of the vanadium present in the fuel to be trapped and to prevent the formation of vanadates having lower Mg/V stoichiometric ratios, notably pyrovanadate (Mg2V20 7 ) or metavanadate (MgV20 6 ) which are not refractory enough to achieve the intended inhibition effect.
  • magnesium orthovanadate (Mg3V20s) which is produced by the following reaction (1):
  • This "parasitic" reaction that forms magnesium sulfate means that in order to trap all the vanadium, a high excess of magnesium with respect to the stoichiometry of reaction (1) has to be added, which, in practice, results in a magnesium/vanadium ratio greater than or equal to 3 in weight.
  • This high excess of magnesium is also useful, not only from a theoretical viewpoint, to ensure the conversion of vanadium into magnesium orthovanadate, but also from a practical viewpoint, to overcome possible inaccuracies or errors related to the in-service determination of the vanadium content of the fuel.
  • the magnesium inhibition treatment can be characterized by the dosing ratio MgO/V20 5 expressed on a molar basis, which will be designated as "m.”
  • This dosing ratio "m” is taken to be equal to 12.6 in the "conventional inhibition” process and is equivalent to the Mg/V ratio of 3 on the previously mentioned weight basis.
  • the corresponding material balance equation is therefore, in practice, written as the following equation (2):
  • s designates the proportion of the excess of magnesium that is converted into sulfate and (1-s) that which is converted into oxide, the number s decreasing with temperature.
  • the main advantage of magnesium inhibition resides in its low cost. Its main drawback resides in the fact that the magnesium-vanadium ashes which are formed by the mineral mix in the right member of equation (3) have a tendency to deposit significantly on the hot parts of the turbine and therefore to foul the latter, thereby gradually decreasing the energy performance of the said turbine. In fact, a substantial fraction of the magnesium-vanadium ashes resulting from this inhibition process deposits itself on the walls of the combustion chambers and on the thermal equipment components located downstream of the latter: this will be referred to as an ash deposition process. This process causes progressive fouling of the thermal equipment as it is operated and entails a correlative and progressive loss of its energy performance (power output and efficiency).
  • Dry cleaning includes introducing into the operating equipment a slightly abrasive material, free of corrosive or ash generating compounds, so as to remove part of the deposits accumulated on the walls of the hot parts.
  • Water washing of the turbine is another, more effective, method to restore performance and includes injecting hot water after shutdown and cool down of the turbine, thereby dissolving the water soluble fraction of the magnesium- vanadium ashes, that is to say, the magnesium sulfate, which results in the destabilization of the entire ash layer and allows the almost complete entrainment of the said deposit; this method therefore allows the initial performance levels to be restored almost completely.
  • a second significant drawback of magnesium inhibition is that it is sensitive to the presence of alkali metals that tend to reduce its effectiveness due to the formation of mixed magnesium and for example sodium vanadates, in particular NaMg4(V0 4 )3, which melts at a temperature above 750°C and therefore lowers the melting point of the magnesium-vanadium ashes, making them more adhesive.
  • this negative effect of alkali metals on the fusibility of the magnesium-vanadium ashes will be designated as the "adverse effect of alkali metals.”
  • a third significant drawback is that at high temperatures magnesium- vanadium deposits become highly fouling which is due, on the one hand, to the partial or complete melting of Mg3V20s (if the temperature locally exceeds 1070°C) and, on the other hand, to the decomposition of the magnesium sulfate into magnesium oxide ("s" tending toward 0 in equations (2) or (3) above), which oxide, being totally insoluble in water, cannot be eliminated by the washing operation. It follows that when the "flame temperature" of the turbine exceeds a limit on the order of 1090°C, the effectiveness of the washing operation becomes very low and restoration of the performance levels problematic: this temperature of 1090°C therefore constitutes the "technical limit" of operation of turbines burning vanadium contaminated fuels.
  • composition of such yttrium-based additives includes at least a stoichiometric amount of yttrium ester having at least four carbon atoms and a hydrocarbon fuel soluble chelating agent that includes 2,4-pentanediene.
  • yttrium-based inhibition has the major advantage that it generates only very small ash deposits on the hot parts of thermal equipment and therefore substantially reduces losses of performance due to fouling inherent in magnesium inhibition.
  • Yttrium also has the advantage that it is a very powerful inhibitor, reaction (4) always prevails over the reaction forming the sulfate Y2(S0 4 )3, and as such requires, in theory, only a mixing ratio Y2O3/V2O5 equal to or slightly greater than the stoichiometric ratio, which, according to reaction (4), is equal to 1 on an atomic basis.
  • s' designates the proportion of the excess of yttrium that is converted into sulfate; s' decreases only very little with temperature, remaining substantially equal to 1 over the temperature range of the inhibition application.
  • the number represented by y is at least equal to 1 and relative excess of yttrium is (y- 1). It is important to note that when y is less than 1, which corresponds to incomplete inhibition, no yttrium sulfate is formed because chemically the formation of vanadate prevails over that of sulfate.
  • a second advantage of yttrium inhibition is the fact that it is insensitive to the presence of alkali metals, because, according to the same patent, it is effective against combined vanadium pentoxide and sodium sulfate corrosion.
  • the drawback of yttrium, as a rare earth metal is its high cost. Once released into the ambient air, vanadium components, like the majority of the so-called “heavy” metals, and in particular vanadium pentoxide V2O5 which is an acid, reactive and “mobile” oxide, do not have a neutral impact on the environment.
  • yttrium used in default with respect to the vanadium yttrium being an expensive metal but capable of minimizing losses of performance due to fouling of the hot parts and moreover free of environmental impact by aqueous media because it is used in default
  • magnesium a less expensive metal than yttrium and attenuating the environmental effects of V2O5, but causing significant losses of performance due to fouling of the hot parts.
  • the vanadium corrosion inhibition process according to the present disclosure therefore uses two vanadium inhibitors - yttrium and magnesium - whose combination allows, in addition to effective inhibition of the said vanadium corrosion:
  • this operating criterion will be designed as the minimum operating time between two washes criterion;
  • FIG. 1 illustrates this double point.
  • the turbine performance P which is either the power output (in kW/h), or the efficiency (in %), is a function of time t (in hours).
  • the performance level (3) is the original performance level of this turbine.
  • the performance level (4) is the threshold from which the operator decides to proceed with a washing operation, and is, for example, taken to be equal to 95% of the original performance (3), it being understood that the operator may also choose to wash the turbine after a defined and invariable number of operating hours, which is a less common strategy, as is the case in example 2 below.
  • the time intervals (5), (6), (7) and (8) represent four turbine operating periods for which four different choices for the parameter y are made. These periods are inserted between the washing operations (9) to (13) during which the power output (14) to (18) is zero, but at the end of which the turbine again has a performance level (19) to (23) identical to the original level (3).
  • the value adopted for y is equal to yi, which is the value that ensures an operating period between two washes that is equal to the lower limit T, predetermined by the operator, without exceeding a loss of performance of 5%.
  • this operating period (6) just satisfies the previously defined "minimum operating time between two washes criterion.”
  • the value adopted for y is less than yi so that the duration of this operating period (5) is shorter than T: this operating period (5) does not satisfy the minimum operating time between two washes criterion.
  • the value adopted for y is equal to y 2 , this value ensures, in absolute value, a performance loss rate, represented by the slope (24) that is equal to the upper limit ⁇ predetermined by the operator. In other words, this operating period (7) just satisfies the performance loss minimization criterion.
  • the value adopted for y is greater than y2 so that the performance loss rate over this period (8), which is represented by the slope (25), is less than the performance loss rate ⁇ predetermined by the operator and therefore satisfies, with a certain margin, the performance loss criterion.
  • the operator may, in a prior experience acquisition phase, determine the values of yi and y2 by following, for a given fuel grade, the performance of its machine as a function of the parameter y of the combined inhibition.
  • the above- described Figure 1 has been included in this description for illustration purposes only and does not cover all of the Y and Mg mixtures that are made possible by the present embodiment and that depend on parameters y and m: for example, the following cases could have been envisaged: y > yi ; y ⁇ y 2 ; yi ⁇ y ⁇ y 2 ; 3 ⁇ m ⁇ 12.6; etc.
  • the combined inhibition process according to the present disclosure can therefore be used in multiple implementation methods that result from the choice of the parameters y and m on the one hand, and from the methods of introducing the two inhibitors on the other hand.
  • the present disclosure concerns a process for inhibiting high temperature corrosion of the hot parts of thermal equipment that burns a vanadium- contaminated fuel in the presence or absence of sodium.
  • This process is characterized in that, in a furnace of the said thermal equipment, the following are introduced per mole of vanadium pentoxide formed during combustion:
  • This combined inhibition method has the advantages that with respect to yttrium inhibition as described in U.S. Patent No. 5,637,118, the inhibition cost is reduced and the protection against combined vanadium pentoxide and sodium sulfate corrosion is reinforced. Further, with respect to conventional magnesium inhibition,
  • the fuel is also contaminated with sodium.
  • the thermal equipment is a gas turbine whose flame temperature is less than, equal to or greater than 1090°C.
  • two separate inhibitors based on yttrium and magnesium precursors respectively can be used.
  • the yttrium oxide is generated from a fat soluble or water soluble precursor, the said precursor being contained in an additive called yttrium-based inhibitor.
  • the magnesium oxide is generated from a fat soluble or water soluble precursor, the said precursor being contained in an additive called magnesium-based inhibitor.
  • an inhibitor combining these two precursors can be used, the additives concerned may be water soluble or fat soluble.
  • the additives concerned may be water soluble or fat soluble.
  • the precursor of the yttrium oxide is preferably yttrium nitrate, an yttrium sulfonate, an yttrium carboxylate, an yttrium chloride, or a nanometric yttrium compound in suspension in a hydrophilic or lipophilic solvent, and
  • the precursor of the magnesium oxide is an inorganic magnesium salt, a magnesium sulfonate, a magnesium carboxylate, or a nanometric magnesium compound in suspension in a hydrophilic or lipophilic solvent.
  • one of the two inhibitors is introduced directly into the fuel or into the furnace or, upstream of the furnace, into any of the supply circuits of the furnace of the thermal equipment, and the other inhibitor is introduced at a location different from the first inhibitor, for example by mixing it into the fuel, for example in a mixing, storage or recirculation tank before sending it into any of the supply circuits of the furnace of the thermal equipment.
  • the other inhibitor is introduced at a location different from the first inhibitor, for example by mixing it into the fuel, for example in a mixing, storage or recirculation tank before sending it into any of the supply circuits of the furnace of the thermal equipment.
  • Supply circuits of the thermal equipment furnace are understood to mean, for example, a fuel supply circuit, or a water supply circuit, or a water/fuel oil emulsion circuit, or an atomizing air circuit.
  • direct injection into the furnace is understood to mean that for example an inlet provided for direct injection into the furnace of either a cleaning product or a combustion improvement product, is used.
  • particles are injected to clean the first turbine stages.
  • the injection of any of these two inhibitors is carried out:
  • the parameter y is chosen to be at least equal to 0.9. In this case, the performance losses due to fouling and the emission of magnesium vanadate particles are minimized. In another embodiment, the parameter y is chosen to be at most equal to 0.1. In this case, the inhibition cost is minimized.
  • the number represent by e having a low value, for example equal to 0.1.
  • the parameter y is chosen to be greater than value yi so as to obtain a power loss rate for the thermal equipment that is less than a predetermined limit.
  • the parameter y is chosen to be greater than value y2 so as to obtain an operating time between two consecutive washes of the turbine that is greater than a predetermined limit.
  • the operator observes that the loss of power due to fouling of the turbine takes place at an average rate of 51 kWe per operating hour, which results in an operating time of 5.05/0.051 or approximately 100 hours between two consecutive washes.
  • V 2 0 5 + y Y2O3 + m (0.882-y) MgO - > 2y YV0 4 + (0.07-y) Mg 3 V 2 08 + (0.672-y) (m-3) MgO.
  • magnesium/yttrium based inhibitors the operator uses an aqueous solution containing 2% magnesium in the form of magnesium nitrate and 15.6% yttrium in the form of yttrium nitrate, a solution that is directly injected into the low pressure section of the fuel circuit, via a high speed rotary mixer that ensures the emulsification of this solution in the fuel. Taking into account the high quantities of vanadium to be inhibited, this option of water soluble inhibitors is economically more interesting than the option of fat soluble inhibitors.
  • a lowly contaminated fuel containing 30 mg V per kilogram (or 30/50.9 0.589 milliatom of V per kg fuel), is burned in a gas turbine whose flame temperature is also 1088°C (therefore practically at the 1090°C technical limit level) and which has a power output of 38 MWe (e.g., electrical MW).
  • magnesium orthovanadate causes the emission of magnesium orthovanadate to fall from 446 mg to 112 mg Mg3V20s per kg burned fuel: it is therefore divided by a factor of approximately 4.
  • the operator uses separate magnesium and yttrium inhibitors, both of the fat soluble type: the magnesium-based inhibitor is a magnesium sulfonate solution with 11% magnesium in a heavy aromatic naphtha and the yttrium-based inhibitor is an yttrium octoate solution with 5% yttrium, also in a heavy aromatic naphtha.
  • These inhibitors are injected in online mode into the low-pressure section of the fuel circuit with the aid of two distinct dosing pumps, but at the same point where a single static mixer is installed to ensure their mixing with the fuel.
  • the turbine and the fuel that it burns are identical to those in example 2 above.
  • the operator who initially uses conventional magnesium inhibition has at the turbine inlet a fuel that is free of alkali metals thanks to water washing of the fuel carried out by a fuel treatment system based on centrifugal separators that ensures a residual sodium content of less than 1 ppm in weight at the inlet of the turbine, thereby preventing the adverse effect of metals on fouling of the turbine.
  • the power loss rate due to fouling increases from 21 kWe to 30 kWe, reducing the production and the efficiency of his machine.
  • the power loss rate remains at a level of 15 kW per hour.

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Abstract

L'invention concerne un procédé basé sur l'utilisation combinée d'yttrium et de magnésium pour inhiber la corrosion du vanadium de pièces soumises à des températures élevées d'un équipement thermique. L'utilisation combinée d'yttrium et de magnésium, appliqués dans un rapport yttrium/magnésium variable, par rapport à l'inhibition classique par le magnésium, peut réduire l'émission de vanadate de magnésium et réduire au minimum les pertes de performance dues à l'encrassement des pièces soumises à des températures élevées, y compris en présence de métaux alcalins. En outre, par rapport à l'inhibition à base d'yttrium seul, elle peut réduire les coûts d'inhibition et renforcer la protection contre la corrosion combinée de pentoxyde de vanadium et de sulfate de sodium.
PCT/US2016/064870 2015-12-03 2016-12-03 Inhibiteurs de corrosion du vanadium à base d'yttrium et de magnésium Ceased WO2017096334A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR1561782A FR3044684B1 (fr) 2015-12-03 2015-12-03 Inhibiteurs de la corrosion vanadique a base d'yttrium et de magnesium
FR1561782 2015-12-03
US15/368,483 US10184091B2 (en) 2015-12-03 2016-12-02 Yttrium and magnesium based vanadium corrosion inhibitors
US15/368,483 2016-12-02

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WO2017096334A1 true WO2017096334A1 (fr) 2017-06-08

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2229861A1 (fr) * 1973-05-14 1974-12-13 United Aircraft Corp
US5637118A (en) * 1994-06-30 1997-06-10 United Technologies Corporation Vanadium corrosion inhibitor
WO2004026996A1 (fr) * 2002-09-17 2004-04-01 Systemseparation Sweden Ab Composition d'additif de combustible et sa preparation
FR3004733A1 (fr) * 2013-04-23 2014-10-24 Ge Energy Products France Snc Procede mettant en œuvre des additifs bi-metalliques pour l'inhibition de la corrosion vanadique dans des turbines a gaz
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

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2229861A1 (fr) * 1973-05-14 1974-12-13 United Aircraft Corp
US5637118A (en) * 1994-06-30 1997-06-10 United Technologies Corporation Vanadium corrosion inhibitor
WO2004026996A1 (fr) * 2002-09-17 2004-04-01 Systemseparation Sweden Ab Composition d'additif de combustible et sa preparation
FR3004733A1 (fr) * 2013-04-23 2014-10-24 Ge Energy Products France Snc Procede mettant en œuvre des additifs bi-metalliques pour l'inhibition de la corrosion vanadique dans des turbines a gaz
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

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