CN1271179C - Nickel compound used as vanadium corrosion inhibitor and burning method using it - Google Patents

Nickel compound used as vanadium corrosion inhibitor and burning method using it Download PDF

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Publication number
CN1271179C
CN1271179C CNB011171677A CN01117167A CN1271179C CN 1271179 C CN1271179 C CN 1271179C CN B011171677 A CNB011171677 A CN B011171677A CN 01117167 A CN01117167 A CN 01117167A CN 1271179 C CN1271179 C CN 1271179C
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vanadium
pollution
nickel
subjected
heat power
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CN1330134A (en
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M·莫里勒
E·洛卡
P·斯坦恩美兹
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GE Energy Products France SNC
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GE Energy Products France SNC
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    • 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
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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
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B77/00—Component parts, details or accessories, not otherwise provided for
    • F02B77/04—Cleaning of, preventing corrosion or erosion in, or preventing unwanted deposits in, combustion engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02C—GAS-TURBINE PLANTS; AIR INTAKES FOR JET-PROPULSION PLANTS; CONTROLLING FUEL SUPPLY IN AIR-BREATHING JET-PROPULSION PLANTS
    • F02C7/00—Features, components parts, details or accessories, not provided for in, or of interest apart form groups F02C1/00 - F02C6/00; Air intakes for jet-propulsion plants
    • F02C7/30—Preventing corrosion or unwanted deposits in gas-swept spaces
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    • 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
    • C10L1/125—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof water
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
    • C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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    • F05C2201/00—Metals
    • F05C2201/04—Heavy metals
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    • F05C2201/00—Metals
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Abstract

The invention concerns inhibition of vanadium corrosion of thermal equipment materials burning vanadium-contaminated liquid fuels using nickel compounds. The invention is applicable in particular to liquid fuel combustion in gas turbines.

Description

Nickel compound is as the application of vanadium corrosion inhibitor and use its combustion method
Generally speaking, the present invention relates to suppress the vanadium corrosion that (inhibition) is used to make the material of heat power equipment, incendiary is the liquid fuel that is subjected to pollution of vanadium in described heat power equipment.
Matter oil fuel in can utilizing for example is subjected to the various products of contaminating impurity, from proving favourable economically.
At various heat power equipments, for example the organic vanadium compound that exists in the incendiary liquid fuel in boiler, diesel engine, the steam turbine etc. can cause the high temperature corrosion with the contacted metallic substance of combustion gases.This corrosion, promptly vanadium corrosive severity is according to actual type, operating temperature range, working time and the operational conditions of the type of the metal or alloy of heat power equipment, heat power equipment and become.
Described corrosive occurrence cause is to have formed in the combustion gases derivative of low-melting vanadium, for example Vanadium Pentoxide in FLAKES (V 2O 5) and V 2O 5/ Na 2SO 4Eutectic mixture, described derivative is under the typical temperature condition at the metal part surface place that is paid close attention to, can cause in the fused ionogen, and there is oxygenant, particularly is being present in the oxygen in the flue gas and electrochemical etching takes place down the existence condition of the sulfate ion that formed by the sulphur in the fuel.
By with the infusible compound form with V 2O 5In addition chemistry " removal " can make the corrosive nature of described these vanadium compound be inhibited, thereby the corrodibility fused electrolyte is eliminated.Traditional long-pending but representative of preparation is an alkaline earth salt, and as calcium salt or magnesium salts, the latter uses more general.Under certain condition of temperature and inhibitor ratio, vanadium can form M with described inhibitor 3V 2O 8The ortho-vanadate of the infusibility alkaline-earth metal of type, wherein, M represents alkaline-earth metal.
The ratio of inhibitor must be fully, so that the vanadium in the fuel is removed fully, and prevent to form the chemistry meter than lower vanadate, for example pyrovanadate or metavanadate, the infusibility of the vanadate that described stoichiometric ratio is lower is not enough to the restraining effect that obtains to expect.
The vanadate that is produced by described inhibition method can form the ash content that is suspended in the combustion gases, and its part of ash is deposited on the combustion chamber wall and is positioned on the wall of assembly of combustion equipment in downstream, combustion chamber.This causes combustion equipment to take place to pollute gradually at run duration, and causes the corresponding of its energy response and forfeiture progressively.
Therefore, the equipment of handling in order to ensure the inhibitor that adopts described vanadium normally moves, and must as far as possible fully described settling be removed, and does not increase the economical load of this operation simultaneously again.Therefore, the run down time of the expense of cleaning operation and equipment must be minimum.
Usually the purging method that adopts has two kinds, and is particularly all the more so for steam turbine: dry type is cleaned and water cleans.
Dry type is cleaned the material of abrasive property of having slightly comprise not containing corrosive compound and ash content and is joined in the equipment that keeps running.
The basis that water cleans is that the hot water that does not contain corrosive salt is circulated in the equipment that shuts down.Hot water makes the vitriol MSO that forms simultaneously at run duration and insoluble vanadate 4Dissolving.
The dissolving of described sulfur acid salt face makes with its common all insoluble solid phases, particularly alkaline earth metal vanadate that exist in settling mechanical unstability takes place.Fast rinsing solution with settling be partly dissolved attitude, the suspended state form that is suspended in the washing lotion of part is removed.
In the following description, with the example of magnesium as traditional inhibitor, because the vitriol solubility of magnesium is very good, well the application of calcium is more not extensive in the solubility of industrial ratio such as its vitriol.
Form simultaneously at ortho-vanadate, the formation of sal epsom is considered from the stoichiometric relation of reaction, requires to add significantly excessive magnesium, so that with all vanadium " removal ", in fact, the mass ratio of magnesium and vanadium is more than or equal to 3.
This inhibitor luxus consumption directly produces additional running cost.
And the pollution that can be observed combustion equipment is faster, causes the acceleration of performance to descend, and needs more frequent cleaning, particularly water to clean, and divides operation to guarantee filling apparatus.
Another weak point relevant with the traditional inhibitor that uses alkaline-earth metal-based and particularly magnesium base relates to " degradation (derating) " of employed heat power equipment.The implication of term " degradation " can be regarded as: from the nominal value of related steam turbine model, the flame temperature of carrying out the steam turbine of this inhibition processing must reduce.Described flame temperature is defined within the hot gas temperature of the ingress of steam turbine first step motion blade, and is one of the basic parameter of regulating the energy indexes of steam turbine.
The reason of described " degradation " is at high temperature can observe magnesium generation desulfurization, desulfurization rate during owing to known desulfurization rate and molecular balance is along with the rising of temperature increases, and, water insoluble by the magnesium oxide that desulfurization forms, therefore, surpassing the particular value of temperature of combustion, and when surpassing specific continuous operating time, residual vitriol ratio is not enough to guarantee that the method that adopts water to clean can correctly remove settling in settling.
Air has vanadium and adopts magnesium can make flame temperature be limited in 1100 ℃ scope at present as the fuel of inhibitor in steam turbine, and in addition, this temperature is Mg 3V 2O 8Fusing point.
Nominal flame temperature that the requirement of restriction flame temperature has hindered the use of the steam turbine of modern technologies, the steam turbine of modern technologies to have to be higher than 1100 ℃ from economic angle and the output rating of Geng Gao.Yet the price of its every KW electric power (unit: dollar) is 1100 ℃ steam turbine (being called " E " level machine) height than flame temperature, and therefore, the operation under the flame temperature that reduces of the steam turbine of modern technologies is uneconomic.
In addition, with the maximized purpose of the energy response of steam turbine, when the ultimate value that flame temperature is set in 1100 ℃, but not more during low value, the more desulfurization rapidly of magnesium requires more frequency of flushing operation for especially, and this has reduced the workability of equipment.
Therefore, deficiency in view of traditional inhibitor of being found, as if it is desirable to make the available vanadium corrosion inhibitor that particularly during the fluid combustion that is subjected to pollution of vanadium, can use, the pollution level of heat power equipment is reduced, thereby make heat power equipment, the working efficiency when particularly relating to steam turbine improves.
In addition, also as if it is desirable to very much and can use and under high flame temperature, work aforesaid " degradation " not occurring or only taking place under the condition of minimum degree degradation to produce the new technology steam turbine of better energy output.
Consider that from another angle also seeming better is to realize being subjected to the use of fuel of pollution of vanadium more effective, economic benefit is more remarkable.
At last, as if especially it is desirable to overcome use, the particularly relevant weak point of the use during being subjected to the liquid fuel combustion of pollution of vanadium with traditional inhibitor.
Applicant company has now found that the vanadium corrosion of adopting Ni-based compound to suppress metallic substance, and particularly being subjected to the liquid fuel vanadium corrosion of (even at high temperature working) metallic substance of incendiary heat power equipment therein of pollution of vanadium is possible and particularly advantageous.
Corroding the metallic substance that can be inhibited thus can be any kind, and particularly ferrous material (non-alloying, slightly be alloyed into strong alloying, stainless steel) or superalloy (chromium base and/or Ni-based and/or cobalt-based), the described reason that can be applicable to the metallic substance of any kind is inhibiting essence, wherein, the vanadium of being removed by nickel is removed from the medium as etching reagent.
Term " heat power equipment " can be regarded as the combustion equipment that refers to any kind, as diesel engine, boiler, steam turbine etc.
According to a preferred embodiment of the invention, the metallic substance of steam turbine is protected, and the vanadium corrosion does not take place.
No matter the type of combustion equipment and the type that contains vanadium fuel are how, can substitute with described Ni-based inhibitor in any occasion of alkaline-earth metal-based inhibitor of can using, and the while has overcome the deficiency relevant with the use of alkaline-earth metal-based inhibitor again.
This is because applicant company confirms, the compound of some nickel can be under suitable temperature and stoichiometric condition with fuel in the vanadium that exists combine the ortho-vanadate (Ni that forms nickel 3V 2O 8), the ortho-vanadate of nickel is a kind of infusible and noncorrosive compound, can suppress the high temperature vanadium corrosion of metallic substance.
The typical temperature scope at the material surface place of the heat power equipment that needs protection in formation, opposite with magnesium, nickel can not form vitriol, thereby has just eliminated relevantly with the formation of vitriol, and the ratio of inhibitor must excessive requirement.
Prevent that by what Ni-based inhibitor provided the effect of vanadium corrosive is very effective, because the ortho-vanadate of nickel is not only thermally-stabilised, and in the general temperature range of the surface of the equipment unit that needs protection, even under the condition that has sodium sulfate to exist, still have unreactiveness.
Under similarity condition,, have considerable magnesium and combine low-melting MgSO that formation has potential corrosion with sodium sulfate when magnesium during as inhibitor 4/ Na 2SO 4Eutectic mixture.Therefore, the anti-vanadium corrosive nature of Ni-based inhibitor is better than containing the magnesium inhibitor, especially exists under the condition of sodium more so, and described sodium can enter in the heat power equipment by fuel cladding or by combustion air.
Ni-based compound uses as inhibitor also has the attendant advantages that reduces the soot particle in the heat power equipment by the effect of the atom nickel in the hydrocarbon polymer flame.
Therefore, according to a first aspect of the invention, at least a Ni-based compound be used for suppressing metallic substance, particularly constitute the material of heat power equipment, more especially constitute wherein burning and corroded by the vanadium of superalloy of industrial steam turbine of the liquid fuel of pollution of vanadium.
According to the present invention, described fuel can be the liquid fuel that is subjected to any kind of pollution of vanadium, and particularly is subjected to the fuel of vanadium light contamination, for example, and condensate oil or heavy petroleum fractions oil, or be subjected to the fuel of vanadium severe contamination.In the above two kinds of cases, magnesium can cause the pollution of the especially severe of movable thermoelectric converter as the inhibitor use, thereby the safe operation of thermal machine is worked the mischief.
Can at high temperature carry out according to burning of the present invention, particularly be higher than 1100 ℃, more especially be higher than under 1300 ℃ the temperature and carry out.
This is because the ortho-vanadate (Ni of formed nickel 3V 2O 8) fusing and decomposition temperature be respectively 1300 ℃ and about 2000 ℃.
These characteristics make Ni-based inhibitor have bigger potential range of application than magnesium base inhibitor, these characteristics help to be subjected to the fuel obvious raising of incendiary steam turbine flame temperature therein of pollution of vanadium especially, and make this fuel that burns in more high efficiency new technology steam turbine become possibility.
Suppress vanadium fully and corrode necessary nickel and be at least 1.74 with vanadium minimum mass ratio, preferably this ratio is in the scope of 1.9-2.5: on the one hand, in order that in industrial application, introduce a safety limit; On the other hand, excessive nickel can cause infusible, non-aggressive and play the formation of the nickel oxide of slight abrasive material effect, and described nickel oxide plays the automatically cleaning agent for heat power equipment, and this helps the maintenance of the energy response of described equipment.The ratio of adjusting nickel and vanadium can be regulated this automatic cleaning action of described inhibitor.
In addition, finding, in described scope, is half of the ash amount that formed by magnesio compound by the ash amount of Ni-based compound formation at least.
This point especially can be by under near the temperature and velocity conditions of the combustion gases the parts that will protect, the non-adhesive matter of Ni-based ash content particle and illustrated by the slight abrasive properties of these particles that are tending towards the newborn settling on the fixing and moving parts surface of heat power equipment is washed away.
Therefore as a result, the frequency of heat power equipment being carried out cleaning operation greatly reduces, and the production efficiency of described heat power equipment is higher.
Adding method and traditional inhibitor of described Ni-based inhibitor are similar.It can be used as the formation adding of the mixture of the liquid fuel in direct and the retention tank with the liposoluble additive, perhaps adds by pipeline before fuel is injected the combustion chamber.It also can adopt before injecting the combustion chamber in the form of pipeline liquid fuel within emulsive water-soluble additive, perhaps injected heat power equipment separately.
Be added into the method for liquid fuel according to described Ni-based compound, it provides form can be liposoluble or water-soluble form, with water-in-oil or oil-in-water emulsion or microemulsion form, perhaps suspensoid form.
When providing with the liposoluble form, described Ni-based compound especially is selected from the organometallic compound that is dissolved in the organic solvent compatible with liquid fuel, for example, the sulfonate, carboxylate salt or the alkanoate that have the nickel of the variable hydrocarbon chain that contains 2-12 carbon atom and be preferably 6 or 7 carbon atoms.
When adopting water-soluble form, described Ni-based compound is especially by the organic or inorganic nickel salt, as the aqueous solution formation of nitrate, vitriol etc.
When adopting water-in-oil emulsion or microemulsion form, the form of described Ni-based compound is a kind of by at least a organic or inorganic nickel salt, the aqueous solution that constitutes of nitrate or vitriol for example, described nickel salt is emulsified in the solvent compatible with pending fuel by the emulsifying agent with suitable hydrophil lipophil balance, and described emulsifying agent is for example for having general form CH 3-(CH 2) 8-(C 6H 4)-O-(CH 2CH 2O) nH is with the polyethoxylated nonylphenol of proper concn adding.The necessary emulsion permanent stability of industrial application can be strengthened as oleic acid by adding a spot of solubility promoter.
When adopting O/w emulsion or microemulsion form, the form of described Ni-based compound is the organic solution that is emulsified in sulfonate, carboxylate salt or the alkanoate of the nickel in the aqueous solution by emulsifying agent, described emulsifying agent has the suitable hydrophil lipophil balance of aforementioned type, and adds with proper concn.Solubility promoter also can add wherein.
When adopting suspension form, described Ni-based compound is a kind of solid compounds, the oxide compound of nickel for example, partially hydrated oxide compound, oxyhydroxide or super base (superbase), described compound is suspended in the aqueous solution or the organic solvent compatible with pending fuel with particle form.
The compound of the nickel of often preferred liposoluble form, it can directly use and be miscible easily with pending fuel.
Because nickel reactive high to vanadium, therefore might be according to concrete enforcement of the present invention, with itself and one or more other metallic combination, with the form of mixtures use of arbitrary proportion.Therefore, can imagine and at least a or several combinations with metal that especially is selected from chromium, silicon, aluminium and magnesium of other effect of corrosion inhibition.Also can imagine and at least a or several combinations with metal that especially is selected from iron and manganese of combustion catalysis.
According to another embodiment of the invention, be subjected to the fuel of pollution of vanadium also to comprise the important metal pollutant that nickel is done.
The use of Ni-based inhibitor makes the natural burning that contains the fuel of nickel to carry out especially economically.This is because the inhibiting nickel amount that rises that should add only is equivalent to and the expectation of nickel and the vanadium difference than the natural concentration of nickel in corresponding concentration and the fuel, the example of this fuel that can mention has crude oil and comes from distillation residue in some oil, the nations of China and India Nicaea crude oil for example, " low sulfur waxy resids " of South Asia oil market.
Another aspect of the present invention relates to the fluid combustion method that is subjected to pollution of vanadium, described method also comprises respectively or as Ni-based additive being added to the step of heat power equipment with the mixture of contaminated liquid fuel except that following incendiary known conventional step.
The additional proportion of nickel should make the mass ratio of nickel and pollution vanadium more than or equal to 1.74, and is preferably 1.9-2.5.
More specifically, according to the preferred embodiments of the invention, described method is applied to the combustion processes in the steam turbine.
The non-adhesion refractory properties of Ni-based ash content particle, the low pollution level of consequent components of steam turbine, and need not to form the water soluble sulfate ash content all make be subjected to pollution of vanadium liquid fuel therein the flame temperature of incendiary steam turbine can significantly improve, this just makes the steam turbine with state-of-the-art that service efficiency advantageously is higher, its nominal flame temperature is higher than 1100 ℃, and especially 1300 ℃ of magnitudes.
Ni-based compound can adopt the form of above-mentioned definition to provide, and especially should decide according to its addition means, and this can implement according to aforesaid traditional method.
Liquid fuel can be the type of the liquid fuel that is subjected to pollution of vanadium, the especially ubi supra of any kind.
The specific embodiments of the method according to this invention, the described fluid combustion method of pollution of vanadium that is subjected to also comprises the step that filters Ni-based ash content.
The simple flushing of the chemical filtering of ash content rather than water makes that the clean conditions of the thermal part of steam turbine can reach best when cleaning end, and the result can make the energy response of steam turbine in operation circulation subsequently be improved.
According to this embodiment, for example may accumulate on that particularly possible the Ni-based settling in the steam turbine can be by being removed based on reducing organic acid solution through the heat power equipment of non-stop-machine long-term operation.Described reductibility organic acid is formic acid or oxalic acid preferably, and it can use under heating condition, and can add the acid inhibitor of carbon steel and cast iron, for example, and the optional thiocarbamide that is added with benzotriazole or tolyl-triazole.
For the present invention is described, below two embodiments are described.
First embodiment
In traditional what is called " s-generation " or " E " level steam turbine, burnt by the astatki of vanadium severe contamination.Term " E " level steam turbine can be regarded as the steam turbine of the flame internal layer temperature of combustion that refers to nominal flame temperature with 1100-1150 ℃ and 2100-2200 ℃, employed astatki is that oil carries out the residue that air distillation produces, and it contains the vanadium of 70-100ppm.
According to the present invention, in order to suppress the vanadium corrosion, with adopting metal-free content is that the nitrate aqueous solution of tensio-active agent emulsive nickel in a kind of organic solvent of 10% of nickel quality is added in the liquid fuel, described organic solvent is made of the middle oil distillations of kerosene type, and with treat that the incendiary oil fuel is miscible.Adopt the high-pressure section of volume pump with the nitrate emulsion injection liquid fuel loop of described nickel, more specifically, inject the upstream of high pressure filter, the amount of the nitrate emulsion of the nickel that control is injected is so that the ratio of nickel and vanadium is 2.
Can find, nickel is applied to be subjected in " E " level steam turbine the burning of the low-volatility fuel of vanadium severe contamination as inhibitor of the present invention, the degree that can make ash-deposition reduces by 2.5 times when adopting magnesium as inhibitor, and this representative consumes same fuel can make average electric power save 4% magnitude.For the annual value of production of 500 ten thousand dollars (that is, being equivalent to the FRF of 35M in May, 2000), this saving amount can be estimated as about 200,000 dollars (that is, being equivalent to the FRF of 1.4M in May, 2000), and this is a considerable result.
Adopt the chemical leaching step of Ni-based ash content to make that the clean conditions of the thermal part of steam turbine reaches best when cleaning end, and the result make that the energy response of steam turbine is improved in working cycle subsequently.
And because the steam turbine continuous operating time between twice adjacent cleaning operation increases to 2.5 times, the result makes heat power equipment have higher working efficiency.The result has also just eliminated the accumulation shutdown period in 1000 hours interior 60 hours of cycle, and 6% production efficiency is saved in this representative.
Second embodiment
In so-called " third generation " or " F " level steam turbine, burnt by " condensate oil " of vanadium utmost point light contamination." F " steam turbine is steam turbine of new generation a kind of who has about 1300 ℃ flame temperature and have 2300-2400 ℃ flame internal layer temperature of combustion who mentions hereinbefore.Used fuel quite originates from gasser, (removes H through optional stabilization (vapour pressure being descended by single flash) and desulfurization 2S) after the processing, condensable at normal temperatures and pressures part.Described condensate oil typically can contain the vanadium of 0.2-1.5ppm.
Use with the preceding fast method of the application in the method for identical nickel compound and identical adding steam turbine.
It should be noted, condensate oil often contains a spot of vanadium, described vanadium amount or exceed steam turbine operation in the time of needn't using corrosion inhibitor allow standard (as 0.5ppm), perhaps, do not allow standard even exceed this, when not adding inhibitor, also can reduce the life-span of the active heated element in the machine, because traditional inhibitor, particularly magnesium base inhibitor, under high flame temperature as one of feature of " F " level steam turbine, can form can not be by washing the stone settling of being removed, therefore, this operation of a machine will inevitably cause the irreversible pollution of blade, and this pollution requires the machine dismounting is manually cleaned.In addition, the ortho-vanadate of magnesium begins fusing at 1100 ℃, and afterwards, its erosion-resisting provide protection begins open to suspicion.When using according to Ni-based inhibitor of the present invention, these serious deficiencies have not existed.
Can obtain similar result if adopt heavier petroleum fraction to act as a fuel, the fuel of such light contamination typically also comprises the vanadium of 0.2-1.5ppm.

Claims (14)

1. Ni-based compound is used to suppress the vanadium corrosive of described metallic substance and uses when the liquid fuel that is subjected to pollution of vanadium burns in the metallic substance heat power equipment.
2. according to the application of claim 1, it is applied to be subjected to the high-temp combustion process of the liquid fuel of pollution of vanadium.
3. according to the application of claim 1 or 2, wherein, the mass ratio of nickel and pollution vanadium is more than or equal to 1.74.
4. according to the application of claim 3, wherein, nickel is 1.9-2.5 with the mass ratio that pollutes vanadium.
5. according to any one the application among the claim 1-4, wherein, the form that provides of described Ni-based compound can be liposoluble or water-soluble form, with water-in-oil or oil-in-water emulsion or microemulsion form, perhaps with water suspension or organic suspension bodily form formula.
6. according to any one the application among the claim 1-5, wherein, described Ni-based compound is with form of mixtures and at least a other metallic combination of any ratio.
7. according to the application of claim 6, wherein, described other metal is selected from chromium, silicon, aluminium, magnesium, iron and manganese.
8. according to any one the application among the claim 1-7, wherein, described liquid fuel is to comprise the fuel of nickel as the important meals pollutent.
9. be subjected to pollution of vanadium and in the metallic substance heat power equipment incendiary fluid combustion method, comprise at least a Ni-based additive is added step in the described heat power equipment.
10. according to the fluid combustion method that is subjected to pollution of vanadium of claim 9, wherein, the mass ratio of nickel and pollution vanadium is more than or equal to 1.74.
11. according to the fluid combustion method that is subjected to pollution of vanadium of claim 10, wherein, nickel is 1.9-2.5 with the mass ratio that pollutes vanadium.
12. according to each the fluid combustion method that is subjected to pollution of vanadium among the claim 9-11, wherein, described heat power equipment is a steam turbine.
13. according to the fluid combustion method that is subjected to pollution of vanadium of claim 12, wherein, described heat power equipment is that flame temperature is higher than 1100 ℃ steam turbine.
14., comprise that a kind of leaching of adopting reductibility organic acid or its esters removes the step of Ni-based ash content according to any one the fluid combustion method that is subjected to pollution of vanadium among the claim 9-12.
CNB011171677A 2000-06-19 2001-04-27 Nickel compound used as vanadium corrosion inhibitor and burning method using it Expired - Fee Related CN1271179C (en)

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FR0007806A FR2810341B1 (en) 2000-06-19 2000-06-19 USE OF NICKEL COMPOUNDS AS VANADIC CORROSION INHIBITORS AND COMBUSTION METHOD USING SUCH NICKEL COMPOUNDS
FR0007806 2000-06-19

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WO2016162718A1 (en) * 2015-04-10 2016-10-13 Ge Energy Products France Snc Method of operating a gas turbine with yttrium and/or magnesium injection
US10577553B2 (en) * 2017-08-09 2020-03-03 General Electric Company Water based product for treating vanadium rich oils

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CN1330134A (en) 2002-01-09
FR2810341B1 (en) 2003-03-28
EP1292656A1 (en) 2003-03-19
MA25946A1 (en) 2003-12-31

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