US20150083165A1 - Suspensions of inorganic cleaning agents - Google Patents

Suspensions of inorganic cleaning agents Download PDF

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Publication number
US20150083165A1
US20150083165A1 US14/224,159 US201414224159A US2015083165A1 US 20150083165 A1 US20150083165 A1 US 20150083165A1 US 201414224159 A US201414224159 A US 201414224159A US 2015083165 A1 US2015083165 A1 US 2015083165A1
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cleaning agent
additive
turbine
agent composition
liquid carrier
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Michel Moliere
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General Electric Co
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General Electric Co
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0013—Liquid compositions with insoluble particles in suspension
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1226—Phosphorus containing
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/20—Water-insoluble oxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/20—Industrial or commercial equipment, e.g. reactors, tubes or engines

Definitions

  • the present invention is directed to a group of cleaning agents that includes solid inorganic particles suspended in liquids and methods of their use.
  • the cleaning agents are configured to be sprayed on the walls of fouled mechanical parts, such as those in combustion equipment, in order to remove the deposits thereof without causing any erosion effect.
  • a turbine mainly comprises of: an air compressor, a combustion system, and an expansion turbine.
  • the hot parts of the turbine are those parts that are in contact with the combustion gases, and mainly include: the parts forming the combustion system (fuel nozzles; liners; transition pieces etc.) and the components of the expansion turbine: “vanes” (fixed blades) and “buckets” (rotating blades).
  • These hot parts are made of metal superalloys (e.g., nickel-based superalloys) and can have ceramic coatings (e.g., anti-corrosion coatings serving as thermal barriers).
  • heavy oils often contain calcium that forms deposits of calcium sulphate (CaSO 4 ) that is considered difficult to remove, as well as vanadium, an element which, once treated with magnesium to inhibit its corrosive effects, forms magnesium vanadate and potentially some magnesium oxide (MgO) that has also a fouling effect.
  • Some primary biomass fuels (“biofuels” and “biogas”) are also likely to generate ashes in combustion equipment.
  • Some process gases also likely to generate ashes in combustion equipment, such as coke-oven gases, blast-furnace gases, or syngas fuels resulting from the gasification of a large variety of solids (e.g., coals; lignite; diverse biomasses; heavy fuels; residue of sewage treatment plants; etc.).
  • this injection must be performed through a certain number (“N i ”) of points of the turbine that must be judiciously distributed in a portion upstream of the hot gas path. These points are generally located around the combustion system in such a way that the injected cleaning agent reaches the highest possible fraction of surface of the hot parts.
  • N i N c .
  • graphite remains a very soft and relatively light solid, with a hardness that is relatively low (about 1.5 on the Mohs scale). Though its hardness exceeds that of bambooous materials, it hardly exceeds that of talc, the softest inorganic material (rated 1 in the Mohs scale). Additionally, graphite's hardness is much lower than that of the inorganic phases found in typical ash deposits, such as magnesium oxide (about 7 on the Mohs scale) and calcium sulphate as gypsum (about 3 on the Mohs scale).
  • graphite's density (in the order of 2.15) is much lower than that of most ordinary inorganics such as iron oxides (approximately 5.5); titanium oxide (approximately 5.5), or aluminosilicates (approximately 6).
  • suspensions must have stability durations substantially higher than their residence time in the circuit via which they are injected (e.g., residence time on the order of one minute).
  • residence time e.g., residence time on the order of one minute.
  • a minimum stability period of 30 minutes will be taken as a conservative criteria.
  • Such objective of stability assumes that the particles do not exceed a maximum size which, in the current state of technology of suspensions, will not exceed a few hundred micrometers.
  • the cleaning agent composition comprises a liquid carrier and a descaling material suspending in the liquid carrier.
  • the descaling material comprises, in one particular embodiment, at least one oxide, in an anhydrous or a hydrated form, that is derived from calcium, magnesium, titanium, iron, aluminium, silicon in the form of silicates having non-fibrous structures, or phosphorus in the form of alkaline-earth phosphates.
  • the cleaning agent comprises a liquid carrier, and a descaling material suspending in the liquid carrier.
  • the descaling material can include at least one oxide, in an anhydrous or a hydrated form, that is derived from calcium, magnesium, titanium, iron, aluminium, silicon in the form of silicates having non-fibrous structures, or phosphorus in the form of alkaline-earth phosphates.
  • the descaling material has, in certain embodiments, a sub-millimeter particle size that is about 5 ⁇ m to about 315 ⁇ m.
  • FIG. 1 is a schematic cross sectional side view of an exemplary gas turbine suitable for use with the cleaning agent described herein.
  • the “hot parts” of a combustion equipment are those of its components which are in contact with the combustion gases.
  • gas turbines or “turbines” will be taken as paradigms of such combustion equipment.
  • the term “powder” and the adjective “powdery” refer to any solid being in a divided state irrespectively to its particle size distribution.
  • oxide combinations refers to any chemical association—binary, ternary, or whichever—of metal oxides or metalloids.
  • perovskite CaTiO 3
  • diopside Ca 2 MgSi 2 O 6
  • oxides or combination of oxides will also cover mixtures of oxides or “associations of oxides” as they have just been defined, as, for example, a mixture of perovskite and diopside.
  • hot gas path designates the volume within which the combustion gases flow and which is limited by hot parts walls.
  • the upstream portion of the hot gas path is the combustion system which, in modern turbines, has an “annular” or “can-annular” geometry.
  • the “firing temperature” of a turbine is the temperature of the combustion gases at their entry in the expansion turbine, not the temperature which develops in the flames.
  • the efficiency of a turbine increases with its firing temperature which, in contemporaneous models, exceeds 1000° C.
  • a group of solid, refractory, and non-combustible materials are generally provided. Such materials, whose combined physical and mechanical characteristics, enable their use as powdery descaling agents as well as their use within cleaning agent compositions, i.e. which enable their putting in suspension, at sub-millimeter scale, in liquids.
  • the cleaning agents are particular suitable for use in a method of on-line cleaning hot parts of a gas turbine.
  • These “cleaning agents” can particularly be used “on-line”, in any combustion equipment that burns fuels that generate ash particles likely to deposit on the hot parts of the said equipment. They are more particularly used when the combustion gas feature temperature and speed levels that exceed 1000° C. and 10 m/s respectively, as a matter of illustration.
  • FIG. 1 illustrates an example of a gas turbine 10 that may be cleaned utilizing the cleaning agent described herein in at least one component, particularly in the hot gas pas.
  • the gas turbine 10 generally includes a compressor section 12 .
  • the compressor section 12 includes a compressor 14 having a plurality of compressor blades 15 and stator vanes 17 , with the compressor blades 15 attached to the shaft 24 .
  • the compressor includes an inlet 16 that is disposed at an upstream end of the gas turbine 10 .
  • the gas turbine 10 further includes a combustion section 18 having one or more combustors 20 disposed downstream from the compressor section 12 .
  • the gas turbine further includes a turbine section 22 that is downstream from the combustion section 18 .
  • a shaft 24 extends generally axially through the gas turbine 10 .
  • the turbine section 22 generally includes alternating stages of stationary nozzles 26 and turbine rotor blades 28 positioned within the turbine section 22 along an axial centerline 30 of the shaft 24 .
  • An outer casing 32 circumferentially surrounds the alternating stages of stationary nozzles 26 and the turbine rotor blades 28 .
  • An exhaust diffuser 34 is positioned downstream from the turbine section 22 .
  • each compressor blade 15 and rotor blade 28 has a leading edge, a trailing edge, a tip, and a blade root, such as a dovetailed root that is adapted for detachable attachment to a turbine disk.
  • the span of a blade extends from the tip edge to the blade root.
  • the surface of the blade comprehended within the span constitutes the airfoil surface of the turbine airfoil.
  • the airfoil surface is that portion of the turbine airfoil that is exposed to the flow path of air from the turbine inlet through the compressor section of the turbine into the combustion chamber and other portions of the turbine.
  • ambient air 36 or other working fluid is drawn into the inlet 16 of the compressor 14 and is progressively compressed to provide a compressed air 38 to the combustion section 18 .
  • the compressed air 38 flows into the combustion section 18 and is mixed with fuel to form a combustible mixture which is burned in a combustion chamber 40 defined within each combustor 20 , thereby generating a hot gas 42 that flows from the combustion chamber 40 into the turbine section 22 .
  • the hot gas 42 rapidly expands as it flows through the alternating stages of stationary nozzles 26 and turbine rotor blades 28 of the turbine section 22 .
  • Thermal and/or kinetic energy is transferred from the hot gas 42 to each stage of the turbine rotor blades 28 , thereby causing the shaft 24 to rotate and produce mechanical work.
  • the hot gas 42 exits the turbine section 22 and flows through the exhaust diffuser 34 and across a plurality of generally airfoil shaped diffuser struts 44 that are disposed within the exhaust diffuser 34 .
  • the hot gas 42 flowing into the exhaust diffuser 34 from the turbine section 22 has a high level of swirl that is caused by the rotating turbine rotor blades 28 .
  • the diffuser struts 44 are positioned relative to a direction of flow 60 of the hot gas 42 flowing from the turbine section 22 of the gas turbine 10 .
  • the cleaning agent can be injected into the hot gas path at any point or points in the compressor section 12 , the combustion section 18 , and/or the turbine section 22 of the turbine 10 .
  • the cleaning agent can be injected into the hot gas path through the fuel nozzles 21 , such as a mixture with the fuel.
  • cleaning agent injectors 39 can be located within the gas turbine 10 for the injection of the cleaning agent into the hot gas path.
  • the cleaning agent injectors 39 can be positioned in any location within the compressor section 12 , the combustion section 18 , and/or the turbine section 22 to inject the cleaning agent into the hot gas path.
  • a pumping device able to accommodate solid suspensions can be utilized.
  • a centrifugal pump can be utilized that creates sufficient pressure to overcome the pressure in the turbine, which is around 10 to 20 bar.
  • a single-stage pump for example, model TH632A890® of Brinkman Pumps
  • a two-stage one for example, the association, in series, of two models TH632A890® and FH632A89® from the same manufacturer
  • the injection pressure must be great enough in order to spray the cleaning agent, which is introduced through injectors, sharply penetrates the flow of combustion gas which has a strong kinetic energy.
  • the N i lines that connect the pump discharge to the N i injection points can be equipped with devices creating high pressure drops, these pressure drops being identical in the N i lines, so that the slight pressure differences which may exist between these points do not cause differences in the N i injection flows.
  • the abovementioned configuration relying on two pumps in series is recommended to obtain the important discharge pressure required by these devices.
  • These devices can be the injectors themselves.
  • the size criterion the empiric conditions which allow the use of sub-millimeter particles
  • the efficiency criterion the product of the density (“D”) of the descaling material by its Mohs hardness (“H”) be greater than 12; this product will be called the “efficiency factor” and noted “F”, i.e.:
  • the Mohs hardness of the descaling material must be equal to or less than 7 and the efficiency factor F must itself be less than 35 and, i.e.:
  • the oxide has a Mohs hardness that is less than or equal to 7 and an efficiency factor, defined as the product of its density by its Mohs hardness, that is between 12 and 35.
  • composition of the descaling material can include, in minor contents (i.e. less than a few %), other phases than those listed in Table 1, provided that they do not contain elements that are potentially detrimental in terms of corrosiveness and EHS.
  • potentially detrimental elements to be excluded include: alkaline metals; halogens, vanadium, sulphur, lead, phosphorus if not associated with alkaline-earth elements; silicon if in the form of fibrous materials, chromium nickel, selenium, arsenic, antimony, cobalt, barium, cadmium, mercury and the elements having atomic numbers superior to that of mercury, as well as, by way of precaution, the elements having doubtful effects on the environment: manganese, copper, zinc.
  • the substances listed in appended Table 1 particularly suitable descaling materials, and can meet the five criteria that have been defined (i.e., particle size; efficiency; non-erosion; non-corrosiveness, and EHS criteria).
  • the descaling materials have been grouped in six chemical classes: iron oxides; titanium oxides; titanates; silicates; aluminosilicates, and phosphates. It is reminded that, by associating, in a same formulation, inorganics contained in Table 1, one obtains “composite materials” which also meet the criteria.
  • the accurate quantity of descaling material that one needs to inject to complete a cleaning operation, in given operating conditions of a turbine can be determined only through an empirical approach.
  • this invention is not aimed at, and is not in a position to define a priori this quantity because it depends not only on the size, density and hardness of the descaling selected material, as it has been already set out, but also and strongly on three key operation parameters that can greatly vary, i.e.: (1) the “contamination of the fuel” (the nature and concentrations of contaminants that it contains), which determines the chemical nature and properties of ash deposits, (2) the operating period between two cleaning operations which determines the quantity of ash deposited, and (3) the firing temperature which conditions their degree of sintering and consequently their hardness.
  • a new generation gas turbine operating at a firing temperature of 1100° C. can require for its cleaning a mass of particles that is twice greater than that required by a former generation gas turbine operating at 950° C.
  • the turbine operator will thus be led to determine the optimum quantity of cleaning agent to be injected, according to these three parameters and relying for example on the monitoring of the classical performance parameters of the turbine (instant power output; specific fuel consumption; pressure at compressor discharge; etc.).
  • the class of iron oxides in anhydrous or hydrated form, is comprised of: iron oxide (III) or ferric oxide (i.e., Fe 2 O 3 ) that has two polymorphs: ⁇ (hematite) and ⁇ (maghemite); two hydrated allotropic forms of Fe 2 O 3 : goethite ( ⁇ -FeOOH) and lepidocrocite ( ⁇ -FeOOH); iron oxide (II, III), of formula FeO—Fe 2 O 3 or Fe 3 O 4 , which is called magnetite and sometimes also referred to by the terms of spinel or “ferrous-ferric oxide; and finally, iron oxide (II) or ferrous oxide (FeO), called wustite.
  • iron oxide based preparations as cleaning agents is interesting for several reasons. From the physical and mechanical standpoint, the iron derived phases of these preparations have densities approximately twice greater than that of graphite (5.2 g/cm 3 for hematite and magnetite; 4.9 for maghemite) as well as a much greater hardness (5.5 to 6.5 for hematite; 5.5 to 6 for magnetite and maghemite, in the Mohs scale). From a thermal standpoint, these phases are refractory components with melting or decomposition temperatures greater than 1500° C. and are totally non-combustible. From an economic standpoint, they are widespread and inexpensive materials that are used for instance as pigments in the paint industry (“red or yellow pigments”) or are available, as good purity by-products from the steel industry. Finally, these particles are totally benign from an environmental standpoint.
  • iron oxide preparations can be dispersed in a combustible or non-combustible liquid medium, such as shown in the examples discussed below.
  • Wollastonite is a calcium silicate mineral (CaSiO 3 ) that may contain small amounts of iron and/or magnesium substituting for calcium. It is a natural mineral, boasting a good refractoriness (melting point of about 1540° C.), and a good absorption capacity of liquids, which favours the stability of suspensions that one can carry out. Moreover, it is economically interesting as widespread “filler” in the manufacturing of paints. Its use will be illustrated in the third example of application given below.
  • kyanite which has an average Mohs hardness of 5.5 and an efficiency factor of 19.5 is also interesting as it has a high fracture modulus and a low scaling rate which helps the fragmentation of the impacted deposits.
  • inorganic material as a structural ceramic component, it also represents an economically interesting descaling material.
  • a distribution of particles in the cleaning agent can have a lower size value of a few micrometers (e.g., 5 ⁇ m) and an upper size value in the order of 315 ⁇ m.
  • the value of the lower size value which is not an essential data in the descaling process is merely given for guidance in order to provide a sufficient definition of the object of the invention and is not likely to restrict the field and reach of the invention.
  • the upper size of 315 ⁇ m which corresponds to the sieve No 26 of standard NFX 11.501 (and, approximately, to the sieve No. 50 of the standard ASTM E11 that equals 297 ⁇ m), must also be taken as an order of magnitude. That is, the indication of this precise value does not either restrict the reach of the invention.
  • sub-millimeter descaling materials i.e. particles not exceeding in size a maximum size taken equal to approximately 315 ⁇ m
  • a “rough descaling material” having for example a “peri-millimeter size”, to which one can apply one of the following treatments: (a) sieved to retain only the sub-millimeter particles; dry crushed and sieved in order to retain only the sub-millimeter particles; or (c) crushed in mixture with the liquid carrier itself (“in-situ crushing”), followed by filtering the obtained slurry to a sub-millimeter size.
  • the cleaning agent composition comprises at least one descaling material selected from the following inorganics: hematite; maghemite; goethite; lepidocrocite; magnetite; wustite; rutile; anatase; brookite; geikielite; perovskite; ilmenite; wollastonite; larnite; enstatite; akermanite; diopside; merwinite; monticellite; fosterite; fayalite; andradite; andalousite; kyanite; sillimanite; mullite; anorthite; ghelenite; hydroxyapatite; or mixtures thereof.
  • descaling material selected from the following inorganics: hematite; maghemite; goethite; lepidocrocite; magnetite; wustite; rutile; anatase; brookite; geikielite; pe
  • cleaning agent composition is formed from a suspension of the descaling material(s) in a liquid carrier.
  • cleaning agent can include:
  • a liquid carrier which is either hydrophilic (water; alcohols or polyols, polyethylene-glycols, polyethers, mixed or not with water; etc.) or eventually lipophilic (aliphatic hydrocarbons, aromatics; alcohols; ketones; white spirit; etc.); this liquid can be a mixture of liquids; its viscosity can be selected to enhance the stability of the suspension; and
  • Such dispersing additives generally have multiple ionic or polar groups, which, by adsorbing on the surface of the particles, prevent them to contact each other due to electrostatic repulsion forces or by steric effect. Thus, such dispersing additives prevent coalescence and subsequent decantation of the descaling material.
  • Suitable dispersing additives include those having ammonium or amine as counter-ion; fatty acid amines; polycarboxylic acids (e.g., ammonium polycarboxylates or amine polycarboxylates); polyamides; polyesters; polyurethanes; sequential copolymers or with “comb polymer structures” based on ether or acrylic groups; etc.; or mixtures thereof.
  • suitable dispersing additive exclude polysiloxanes that are likely to release free silica during combustion; anionic dispersants whose counter-ions are metals (alkaline metals). Additionally, polyols, polyethylene-glycols, and polyethers, even though they present intrinsic dispersing properties, are not classified in this document as dispersing additives because they are in general introduced in substantial proportions and are an integral part of the base liquid.
  • processing additives may be included in the cleaning agent composition, such as: viscosity modifier additives (i.e. allowing the increase or reduction of the viscosity and optimize the stability of the suspension or facilitate its pumping); anti-foam additives (non-silicone substances to avoid the release of free silica during combustion); biocide additives; anti-freeze additives, etc., or mixtures thereof.
  • viscosity modifier additives i.e. allowing the increase or reduction of the viscosity and optimize the stability of the suspension or facilitate its pumping
  • anti-foam additives non-silicone substances to avoid the release of free silica during combustion
  • biocide additives i.e. allowing the increase or reduction of the viscosity and optimize the stability of the suspension or facilitate its pumping
  • biocide additives i.e. allowing the increase or reduction of the viscosity and optimize the stability of the suspension or facilitate its pumping
  • biocide additives i.e. allowing the increase or reduction
  • the abovementioned additives will be preferably of the organic type to avoid the generation of ash. All of the components, but for the descaling material, generally constitute the “liquid carrier.”
  • the obtained descaling material is mixed with the liquid carrier, which leads to a “finished” cleaning agent.
  • a “semi-finished” cleaning agent is first formed (“semi” meaning a filtration is yet to be carried out), and then a “finished” cleaning agent is formed after filtering at the sub-millimeter level.
  • This “in-situ crushing” operation which can be preferably carried out in the presence of wetting agents, represents a well-known preparation mode of suspensions (or “slips”) in the ceramic industry. That is, it is known that during the fragmentation of particles, the molecules of the wetting agents are easily absorbed on the surface of the freshly formed fragments, which enhances their dispersing effect.
  • the liquid carrier is water-based
  • its vaporization when introduced in the combustion system tends to lower the temperature of the combustion gases which is likely to disturb the combustion process and the control of the turbine operation.
  • polyethylene glycol (PEG) can be added to the water-based liquid.
  • PEG has the double advantage of having a dispersing effect and boasting a moderate combustion heat (23700 kJ/kg).
  • PEG can be incorporated in concentration such that this combustion heat compensates approximately the latent heat of water vaporization (2260 kJ/kg).
  • the vaporization of the so addivated cleaning agent will be neither endothermal, nor exothermal but “athermal” and will not disturb the combustion process nor the turbine operation.
  • This “athermal” condition can be realized for a PEG content in the order of 10% in mass.
  • the performance of a cleaning operation depends, for a type of defined deposit, on six parameters: (i) the mass of the injected cleaning agent, a parameter under operator's control; (ii) the hardness of the particles; (iii) their density (defined as a bulk property); (iv) their size; (v) the speed; and (vi) the firing temperature.
  • the hardness, density, and size of the particles are intrinsic properties of the material used, while the speed and firing temperature depend on the turbine model and its operating conditions and are thus imposed by the application.
  • the cleaning efficiency increases as the first five parameters increase but decreases when the sixth one, the firing temperature, increases. It must be noted that relatively low-size particles (i.e., less than 1 ⁇ m or a few micrometers) have a negligible descaling effect.
  • the mass of cleaning agent that must be injected on-line to descale a defined type of deposit, formed in an application which is itself defined, depends on the hardness, density and size of the particles constituting this cleaning agent. To limit the costs of the cleaning operation and reduce the emission of particles at the turbine exhaust, this quantity must be reduced.
  • a rough descaling material which is a magnetite powder constituted by an iron inorganic provided by Rana Gruber (Norway), called “magnetite concentrate” and whose brand name is M-150T®.
  • This inorganic material contains 99% of magnetite and has a density of 5.2 g/dm3 and a Mohs hardness of 5.5 to 6, whereby its efficiency factor is in the order of 30.
  • the finished cleaning agent thus obtained contains only minute traces of corrosive elements (alkaline metal content of magnetite M-150T: less than 0.2%) knowing that care has been taken to discard from the formulation anionic dispersants as well as elements that are detrimental to health and environment (bromine being present only as traces).
  • This cleaning treatment enables recovering 7.3% of the power output, which corresponds to a recovery rate of approximately 91% of the power loss which was caused by the accumulation of magnesium/vanadium ash on the turbine hot parts.
  • the injection of 50 kg of a biomass material based cleaning agent (fragments of apricot cores) provides a recovery of only 1.7% of the power lost by fouling (recovery rate of 21%).
  • the cleaning agent is also an “iron oxide based preparation” whose rough descaling material is this time a hematite based inorganic (Fe 2 O 3 ) procured from the same supplier and called “hematite concentrate H-400®”.
  • the mass composition of this inorganic is: 90% hematite, 5% water; the other minor components are SiO 2 , Al 2 O 3 and CaO (in the form of calcium aluminosilicates that are EHS compliant).
  • Hematite has a density of 5.25, a hardness of 5.5-6 and an average efficiency factor of 31.5.
  • liquid carrier is made as in example No 1: one puts and mixes in a tank, using a paddle stirrer, the liquid carrier and the previously crushed H-400 material in a mass ratio of 85/25.
  • the so prepared cleaning agent contains only minute traces of corrosive elements (alkaline metal content of magnetite H-400: less than 0.2%) knowing that care has also been taken to discard from the formulation anionic dispersants as well as elements that are detrimental to health and environment (bromine being present only as traces).
  • This injection is carried out under a pressure of approximately 28 bars, with a constant total flow of 10 l/mn, through ten identical high-pressure injectors that allow to uniformly distributing the injection to the ten combustion chambers of the turbine, so that the descaling material reaches the largest possible surface fraction of the hot parts.
  • This treatment allows recovering 8.5% of power output, which corresponds to 94% of the power loss which was “lost” by fouling.
  • the rough descaling material is the inorganic material NYCOR R® (supplier: NYCO, USA) containing 98% of wollastonite, the remaining 2% not containing detrimental elements.
  • This inorganic has a particle size range that goes up to 700-800 ⁇ m: one decides to proceed with an “in-situ crushing”.
  • the following mixture is prepared (percentages are given in mass): 30% of NYCOR R®; 8% of “polyglycol 200” (PEG 200); 6% of Dispersogen FA® (non-ionic dispersing additive; supplier: Clariant); 4% of Genamin CC 100® (cationic, ammonia-based, dispersing additive; supplier: Clariant); 0.3% of acetic acid (shear-thinning-additive); 0.3% of Efka 2526® (organic anti-foam additive; suppliers: BASF); 0.2% of Myacid S2® (biocide additive; suppliers: BASF); and the balance: deionised water (51.2%).
  • This treatment enables the recovery of 6% of power, which corresponds to the collection of approximately 86% of the power output loss caused by the accumulation of magnesium/vanadium ash on the hot parts of the turbine.

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US20140315136A1 (en) * 2013-04-23 2014-10-23 General Electric Company Methods of operating a gas turbine to inhibit vanadium corrosion
US20150300263A1 (en) * 2014-04-22 2015-10-22 Ge Energy Products France Snc Method of operating a gas turbine engine burning vanadium-contaminated liquid fuel
CN106958026A (zh) * 2017-05-04 2017-07-18 中国第汽车股份有限公司 一种可低温条件下使用的中性除锈剂
US20170254218A1 (en) * 2016-03-01 2017-09-07 General Electric Company System and Method for Cleaning Gas Turbine Engine Components
US20170254217A1 (en) * 2016-03-01 2017-09-07 General Electric Company Dry Detergent For Cleaning Gas Turbine Engine Components
US20190048279A1 (en) * 2017-08-09 2019-02-14 General Electric Company Water based product for treating vanadium rich oils
US20200248583A1 (en) * 2015-12-11 2020-08-06 General Electric Company Meta-stable detergent based foam cleaning system and method for gas turbine engines
US11692155B1 (en) 2022-05-16 2023-07-04 University Of Houston System Nano-micro particle fluid for cleaning dirty and greasy surfaces and pipes
WO2023224598A1 (fr) * 2022-05-16 2023-11-23 University Of Houston System Fluide a nano-micro particules pour nettoyer des surfaces et conduites sales et graisseuses

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9556393B2 (en) * 2013-04-23 2017-01-31 General Electric Company Methods of operating a gas turbine to inhibit vanadium corrosion
US20140315136A1 (en) * 2013-04-23 2014-10-23 General Electric Company Methods of operating a gas turbine to inhibit vanadium corrosion
US20150300263A1 (en) * 2014-04-22 2015-10-22 Ge Energy Products France Snc Method of operating a gas turbine engine burning vanadium-contaminated liquid fuel
US9976488B2 (en) * 2014-04-22 2018-05-22 Ge Energy Products France Snc Method of operating a gas turbine engine burning vanadium-contaminated liquid fuel
US20200248583A1 (en) * 2015-12-11 2020-08-06 General Electric Company Meta-stable detergent based foam cleaning system and method for gas turbine engines
US11591928B2 (en) * 2015-12-11 2023-02-28 General Electric Company Meta-stable detergent based foam cleaning system and method for gas turbine engines
US11415019B2 (en) 2015-12-11 2022-08-16 General Electric Company Meta-stable detergent based foam cleaning system and method for gas turbine engines
US20170254218A1 (en) * 2016-03-01 2017-09-07 General Electric Company System and Method for Cleaning Gas Turbine Engine Components
US20170254217A1 (en) * 2016-03-01 2017-09-07 General Electric Company Dry Detergent For Cleaning Gas Turbine Engine Components
US10323539B2 (en) * 2016-03-01 2019-06-18 General Electric Company System and method for cleaning gas turbine engine components
CN106958026A (zh) * 2017-05-04 2017-07-18 中国第汽车股份有限公司 一种可低温条件下使用的中性除锈剂
US10577553B2 (en) * 2017-08-09 2020-03-03 General Electric Company Water based product for treating vanadium rich oils
US20190048279A1 (en) * 2017-08-09 2019-02-14 General Electric Company Water based product for treating vanadium rich oils
US11692155B1 (en) 2022-05-16 2023-07-04 University Of Houston System Nano-micro particle fluid for cleaning dirty and greasy surfaces and pipes
WO2023224598A1 (fr) * 2022-05-16 2023-11-23 University Of Houston System Fluide a nano-micro particules pour nettoyer des surfaces et conduites sales et graisseuses

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