CN108647459A - Assess the method influenced on turbo blade heat erosion when hydrogen sulfide is exceeded in fuel gas - Google Patents

Assess the method influenced on turbo blade heat erosion when hydrogen sulfide is exceeded in fuel gas Download PDF

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CN108647459A
CN108647459A CN201810470935.4A CN201810470935A CN108647459A CN 108647459 A CN108647459 A CN 108647459A CN 201810470935 A CN201810470935 A CN 201810470935A CN 108647459 A CN108647459 A CN 108647459A
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dew point
heat erosion
exceeded
corrosion
fuel
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张超
何建元
孙鹏
潘宏伟
邱中辉
李东明
李卓
赵旭东
吕成林
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Longjiang Broad Sail Gas Turbine Co Ltd
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Longjiang Broad Sail Gas Turbine Co Ltd
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Abstract

Energy source and power technical field of the present invention, and in particular to a method of turbo blade heat erosion is influenced when hydrogen sulfide is exceeded in assessment fuel gas.For predicting heat erosion variation tendency to take corresponding measure to mitigate extent of corrosion.It is the premise that heat erosion occurs that material surface, which forms corrosion product, this will show that the position only under the conditions of temperature is less than dew point and with specified pressure can just face the conclusion of corrosion risk.Based on the calculating to corrosion product dew point, the risk that turbine part faces heat erosion will be illustrated.Under given conditions, the corrosion product dew point curve calculated by thermodynamics method simulation, it is shown that there are the regions of heat erosion risk.Meanwhile dew point will be increased as pressure increases, this will cause more positions to face heat erosion risk.By analyzing influence of the major impurity changes of contents to dew point curve, main affecting factors are confirmed, and then complete in H2To the assessment of turbine blade of gas turbine heat erosion degree in the case of S is exceeded.

Description

Assess the method influenced on turbo blade heat erosion when hydrogen sulfide is exceeded in fuel gas
Technical field：
Energy source and power technical field of the present invention, and in particular to rotten to turbo blade heat when hydrogen sulfide is exceeded in a kind of assessment fuel gas Lose the method influenced.
Background technology：
With the increasing of gas and oil in sea and exploitation dynamics, offshore platform quantity quickly increases therewith, to being opened for marine oil and gas Adopt provide motive power oil production platforms core equipment --- the dependence of Gas Turbine Generating Units is growing day by day.External combustion gas Turbine producer hydrogen sulfide in about gaseous fuel allows have a particular provisions and explanation in the index of content, but concrete reason and Mechanism does not know that correlative study document or data are also seldom but.In order to ensure the domestic combustion gas wheel of platform operation at sea The reliability of machine needs to combine combustion engine operating parameter, to heat when exceeded by hydrogen sulfide in correlation means analysis and assessment fuel gas The influence of corrosion.
High temperature corrosion under gas turbine operation environment can be regarded as the degenerative process that material reacts with combustion gas.It degenerates Process can be divided into two Main Stages：Exhaust gas corrosion and heat erosion（Or appositional pattern corrosion）.Heat erosion, which is formed, to be needed just like sulfuric acid The deposit of salt or chloride exists, they are gathered in material surface and cause and metal fast reaction and be allowed to degenerate.
Heat erosion is considered as " material is at high temperature since melting mineralization forms accelerated oxidation caused by film ".Corrosion The deposition of product such as sulfate is the necessary condition of heat erosion initial period.According to thermodynamical equilibrium phasor, the formation of sulfate Condition can be by being calculated.Other than stability condition of thermodynamics, it is initial that corrosion product is gathered in heat erosion on blade material Stage is also required.
The heat erosion of gas turbine material only can just occur when corrosion product deposits.The appearance of similar corrosion product can be by Dew point thermodynamic simulation obtains.Dew point should be defined as the maximum temperature when depositing generation from the point of view of thermodynamic consideration.Dew Point depends on two kinds of factors of gas component and pressure.The kinetic factors such as deposition rate, aerodynamic feature are herein Do not consider.
Therefore, corrosion-resistant evaluation is carried out to orientation and single crystal high-temperature alloy material for low impurity fuel conditions, can passed through The assessment to corrosion risk is completed to the Thermodynamic Simulation of main corrosion product dew point.
Invention content：
The purpose of the present invention is to propose to a kind of thermodynamics analysis methods, effectively to assess turbo blade hydrogen sulfide in fuel gas exceeded When influence to heat erosion, meet turbine blade of gas turbine under working condition to the requirement of hot corrosion resistance.
The technical solution adopted by the present invention is：To turbo blade heat erosion shadow when hydrogen sulfide is exceeded in a kind of assessment fuel gas Loud method, includes the following steps：
Step 1: the thermodynamics for calculating sulfate and chloride cohesion using the program ChemSage 4.1 for calculating chemical balance is flat Weighing apparatus；Program by the minimization of Gibbs free energyization in chemical reaction system by carrying out calculation of thermodynamic equilibrium, to compound Amount and ingredient are calculated；The thermodynamical equilibrium of sulfate and chloride cohesion is calculated using program ChemSage 4.1, 4.1 programs of ChemSage are derived from SOLGASMIX-PV, and this method is successfully used for the calculating of industry gas turbine Mg-V phases, multiple The amount of compound and ingredient can be calculated in wide temperature and pressure range in miscellaneous reaction system, and calculating process does not consider combustion gas High flow rate and the brief stay time near blade
Step 2: in above-mentioned calculating, generate comprising the data file including C, H, O, N, Ar, S, Cl, Na, K and Ca element, Thermodynamic data is from database SGTE pure material databases（1996 editions）It obtains.
Step 3: simulation ingredient, air and the water in selection fuel are to complete to calculate, the impurity in fuel is individually added into, The total content of impurity is extremely important for the dew point of corrosion product and heat erosion in combustion gas, and gas turbine combustion process is in excess It is carried out in air, also referred to as lean combustion；Usual air fuel ratio is provided in the form of quality, in order to preferably compare, is introduced Parameter lambda indicates that the ratio of excess air, lambda definition are for the air mass flow of stoichiometric(al) combustion and the ratio of actual air flow Value, represents the air mass flow for stoichiometric(al) combustion when λ=1, and when λ=2, which represents, provides twice of air mass flow based on chemical Amount burning, impurity content will be provided in the form of fuel equivalent, and the impurity in fuel is individually added into the form of equivalent；It is counted by simulating Calculate the pressure-dependent Trendline of corrosion product dew point generated, it is shown that there are the regions of heat erosion risk；
Step 4: by analyzing influence of the major impurity changes of contents to dew point curve, main affecting factors are confirmed, and then complete In H2To the assessment of turbine blade of gas turbine heat erosion degree in the case of S is exceeded；Dew point will be increased as pressure increases, this More positions will be caused to face heat erosion risk, therefore analyzed respectively under the conditions of different pressures, sulfur content changes to corruption The affecting laws and chlorine metal that the affecting laws of erosion product dew point variation, alkali metal content variation change corrosion product dew point contain The affecting laws that amount variation changes corrosion product dew point.
Further, the influence of sulfur content calculates Na when sulfur content changes within the scope of 0.01-1wt.%2SO4With K2SO4As shown in Figure 1, when higher than 1.5-1.8bar pressure, dew point will increase dew point curve with the increase of sulfur content, this Kind influences to increase with pressure and reinforce；Na2SO4And K2SO4Dew point with the increased critical point of pressure be respectively 1.8bar and 1.5bar；Less than under critical pressure, dew point only has slight change, under the conditions of 30bar, when sulfur content increases from 0.01wt.% When to 0.1wt.%, Na2SO4And K2SO4Dew point will increase 18K or so, the dew point under the conditions of 0.1wt.% and 1wt.% sulfur contents The only difference of 8K；Under the conditions of 30bar, when sulfur content increases to 1wt.% from 0.01wt.%, Na2SO4And K2SO4Dew point will Increase 26K or so, under the conditions of 1bar, the increased influence of sulfur content is almost negligible to be disregarded, at this time Na2SO4And K2SO4Dew point Each variation 1-3K or so.
Further, the influence of alkali metal content analyzes the variation of Alkali-Metal Na and K contents to corrosion product dew point It influences, Fig. 2 gives the Na under the conditions of different sodium contents2SO4Dew point curve, the variation of alkali metal content to dew point curve have compared with Big to influence, alkali metal content is lower, and corresponding corrosion product dew point is also lower, and sodium content reduces 10 times（From 1ppm to 0.1ppm） Caused dew point variation reduces 100K when being 30bar, when 1bar reduces 80K, the pressure condition condition very low in impurity content Lower effect is not obvious；K2SO4With the variation of alkali metal content on dew point curve influence and Na2SO4It is similar, as shown in figure 3, K2SO4Dew point in same fuel equivalent（wppm）It is less than Na under pollutional condition2SO4。K2SO4The reduction of dew point is with alkali metal content The changing rule and Na of reduction2SO4Unanimously.
Further, the influence of chlorinity, under the conditions of analyzing 0.5ppmNa, 0.5ppmK and 0.1wt.%S, Cl contents point Not Wei 10ppm, 100ppm when Na2SO4And K2SO4The variation characteristic of dew point curve, two kinds of sulfate as shown in Figure 4 is much like, The addition of Cl results in the reduction of dew point, this is because caused by NaCl and KCl is formed in gas phase, part Na and K is with gas phase chlorine The form of compound exists, and can just form corresponding sulfate under the conditions of only having existing for remaining alkali metal, this can reduce gas The content of alkali metal sulfates and dew point is influenced in phase, when Cl contents are 100ppm, Na2SO4Dew point is reduced in 1bar 44K reduces 34K in 30bar；K2SO4The fall of dew point is relatively low, respectively 43K is reduced in 1bar, in 30bar When reduce 28K, pressure is higher, caused by the addition of Cl dew point reduce it is fewer.
Further, when condition be λ=2, Ω=0 when, burn natural gas under the conditions of corrosion product dew point with pressure change Change trend, wherein impurity content（Fuel equivalent）It is set as：0.1wt.% S, 0.5wppm Na, 0.5wppm K.
Beneficial effects of the present invention：For predicting heat erosion variation tendency to take corresponding measure to mitigate extent of corrosion.Material It is the premise that heat erosion occurs that material surface, which forms corrosion product, this will be obtained only in temperature less than dew point and with specified pressure Under the conditions of position can just face the conclusion of corrosion risk.The corrosion product dew point curve calculated by thermodynamics method simulation, Show that, there are the region of heat erosion risk, dew point will be increased as pressure increases, this will cause more positions to face heat Corrosion risk.By analyzing influence of the major impurity changes of contents to dew point curve, main affecting factors are confirmed, and then complete H2To the assessment of turbine blade of gas turbine heat erosion degree in the case of S is exceeded.It is effective to propose a kind of thermodynamics analysis methods Influence of the turbo blade to heat erosion when hydrogen sulfide is exceeded in fuel gas is assessed, meets turbine blade of gas turbine in operating mode item To the requirement of hot corrosion resistance under part.
Description of the drawings：
Fig. 1 is the Na under the conditions of different S contents2SO4And K2SO4Dew point curve；
Fig. 2 is the Na under the conditions of different Na contents2SO4Dew point curve；
Fig. 3 is the K under the conditions of different K contents2SO4Dew point curve；
Fig. 4 is the Na under the conditions of different Cl contents2SO4And K2SO4Dew point curve.
Specific implementation mode：
With reference to the operating parameter and attached drawing of certain type 25MW gas turbines to further instruction of the present invention：
1, for 25MW combustion engine, salt content can be controlled by means and meet K+Na ＜ 0.0015ppm, simultaneously because 0.8 operating mode Under the conditions of air excess factor should be greater than 2, therefore the actual corrosion and heat resistant situation of 25MW combustion engine turbine components should be better than reference The analysis and assessment that Fig. 1 is carried out.H in the fuel used gas of certain offshore platform at present2The exceeded situation of S contents and index request are shown in Table 1.
1 H of table2The exceeded situation and index request of S contents
Gaseous-pressure under 0.8 operating mode before high-pressure turbine is 1.7333MPa, and high-pressure turbine guide vane averga cross section t is flat under 1.0 operating modes It it is 856 DEG C, 842 DEG C of high-pressure turbine movable vane averga cross section t average out to, the corresponding temperature under 0.8 operating mode should be lower.Work as H2S contains When amount reaches 100vppm, the mass fraction of corresponding S is that 0.016wt.% is estimated and corresponded at this time in conjunction with the dew point curve of Fig. 1 Na2SO4Dew point is about at 900 DEG C, K2SO4Dew point of the dew point about under 835 DEG C, actual conditions, which should be less than, estimates temperature, at this time H2S is more corresponding Na than the 15vppm that standard requires in 100vppm2SO4Dew point, which improves, should be not more than 30 DEG C.
To sum up, under the conditions of 0.5ppm Na, 0.5ppm K, high-pressure turbine is dynamic, guide vane will mainly face corrosion product Na2SO4Heat erosion problem caused by deposition, this will high-pressure turbine be dynamic, guide vane surface heat etching condition influencing to a certain degree, Specific extent of corrosion should be compared judgement and analysis according to experimental data.
Gaseous-pressure under 0.8 operating mode before low-pressure turbine is 0.6600MPa, and low-pressure turbine guide vane is averagely cut under 1.0 operating modes 833 DEG C of face t average out to, 766 DEG C of low-pressure turbine movable vane averga cross section t average out to, the corresponding temperature under 0.8 operating mode should be lower.When H2When S contents reach 100vppm, corresponding S mass fractions are that 0.016wt.% is estimated and corresponded at this time in conjunction with the dew point curve of Fig. 1 Na2SO4Dew point is about at 875 DEG C, K2SO4Dew point of the dew point about under 820 DEG C, actual conditions, which should be less than, estimates temperature, this When H2S fused salt dew points more corresponding than the 15vppm that standard requires in 100vppm improve at about 10 DEG C or so.
To sum up, under the conditions of 0.5ppm Na, 0.5ppm K, low-pressure turbine is dynamic, guide vane may face heat erosion risk, but Since dew point amplitude of variation is little, smaller, H is acted on to the heat erosion condition change of blade surface2S is exceeded to metallic matrix or to be oozed Heat erosion lesser extent caused by aluminized coating, and Corrosion Types at this time belong to low temperature hot corrosion, it is desirable that it is higher than 700 in temperature DEG C when SO3Minimum partial pressure（pSO3）Meeting certain condition can just occur.Therefore H2S is exceeded warm caused by low-pressure turbine blade Extent of corrosion is lighter, is influenced less on using.
Gaseous-pressure under 0.8 operating mode before power turbine is 0.3363MPa, and power turbine inlet gas temperature is 721 DEG C （Higher than blade surface temperature）.Work as H2When S contents reach 100vppm, corresponding S mass fractions are 0.016wt.%, in conjunction with Fig. 1's Dew point curve is estimated and corresponds to Na at this time2SO4Dew point is about at 845 DEG C, K2SO4Dew of the dew point about under 790 DEG C, actual conditions Point, which should be less than, estimates temperature, at this time H2S fused salt dew points more corresponding than the 15vppm that standard requires in 100vppm improve about 5 DEG C or so.
To sum up, power turbine is dynamic, guide vane situation is similar with low-pressure turbine, may face heat erosion risk, but due to dew point Only slight change acts on very little to the heat erosion condition change of blade surface, while the formation of low temperature hot corrosion needs SO3's Minimum partial pressure（pSO3）Meet certain condition, therefore H2Heat erosion degree caused by the exceeded possibility to metallic matrix of S is very light, to whirlpool The use of impeller blade influences very little.
2, for 25MW combustion engine, salt content can meet the requirement of K+Na ＜ 0.0015ppm in inlet air, while in view of Air excess factor under 0.8 working condition should be greater than 2, and sulfur content when exceeded is that 0.016 wt.% is also far below 0.1 Wt.%, therefore the actual corrosion and heat resistant situation of 25MW combustion engine turbine components should be much better than the assessment point carried out with reference to Fig. 2 and Fig. 3 Analysis.
According to above-mentioned gaseous-pressure condition, the dew point curve of Fig. 2 and Fig. 3 are respectively referred to, estimates corresponding Na at this time2SO4 Dew point is about at 765 DEG C, K2SO4Dew point of the dew point about under 715 DEG C, actual conditions, which should substantially be less than, estimates temperature.Therefore, Estimated Na2SO4And K2SO4It is average that dew point should substantially be less than high-pressure turbine guide vane, movable vane under 0.8 operating mode described in 3.2.2.1 Section tIt is average。
To sum up, under conditions of K+Na ＜ 0.0015ppm, even if working as H2When S contents reach 100vppm, high-pressure turbine is dynamic, Guide vane will be subject primarily to common high-temperature oxydation effect, will not face sulfate Na2SO4And K2SO4Heat erosion wind caused by deposition Danger.
Low-pressure turbine parts scenarios are similar with high-pressure turbine, i.e., estimated under conditions of K+Na ＜ 0.0015ppm Na2SO4And K2SO4Dew point is substantially less than low-pressure turbine guide vane, movable vane averga cross section t under 0.8 operating modeIt is average.Work as H2S contents When reaching 100vppm, low-pressure turbine is dynamic, guide vane will be subject primarily to common high-temperature oxydation effect, not will produce sulfate deposition Caused heat erosion problem.
Gaseous-pressure under 0.8 operating mode before power turbine is 0.3363MPa, and power turbine inlet gas temperature is 721 DEG C （Higher than blade surface temperature）.The dew point curve for respectively referring to Fig. 2 and Fig. 3 estimates corresponding Na at this time2SO4Dew point about exists 735 DEG C, K2SO4Dew point of the dew point about under 680 DEG C, actual conditions, which should be less than, estimates temperature.Since in low pressure, S contains quantitative change The influence changed to dew point is smaller, therefore for power turbine, and 3-6 grade blades surface temperature is it is possible that less than dew point Situation.
To sum up, the risk that power turbine is dynamic, guide vane needs consideration may face heat erosion, if low temperature hot corrosion forms institute The SO needed3Minimum partial pressure（pSO3）Condition cannot be met, then H2S contents it is exceeded on the use of turbo blade without influence.
For 25MW combustion engine, turbine gaseous-pressure changes 0.3363 between 1.7333MPa, it is assumed that Cl content ranges 10ppm is arrived 0, the dew point variation of corrosion product as can be seen from Figure 4 is no more than 10 DEG C, while in view of the mistake under 0.8 working condition Amount air coefficient λ should be greater than 2, and sulfur content when exceeded is that 0.016 wt.% is also far below 0.1 wt.%.Therefore, when Cl contents from 0 when increasing to 10ppm, and the reduction amplitude of dew point is smaller, and the corrosion and heat resistant situation of Gas Turbine component can slightly become at this time It is good.

Claims (1)

  1. A kind of method that turbo blade heat erosion is influenced when 1. hydrogen sulfide is exceeded in assessment fuel gas, it is characterised in that：Including Following steps：
    Step 1: the thermodynamics for calculating sulfate and chloride cohesion using the program ChemSage 4.1 for calculating chemical balance is flat Weighing apparatus；Program by the minimization of Gibbs free energyization in chemical reaction system by carrying out calculation of thermodynamic equilibrium, to compound Amount and ingredient are calculated；
    Step 2: in above-mentioned calculating, generate comprising the data file including C, H, O, N, Ar, S, Cl, Na, K and Ca element；
    Step 3: simulation ingredient, air and the water in selection fuel are to complete to calculate, the impurity in fuel is individually added into；Usually Air fuel ratio is provided in the form of quality, in order to preferably compare, introduces the ratio that parameter lambda indicates excess air, lambda definition is For the air mass flow of stoichiometric(al) combustion and the ratio of actual air flow, when λ=1, represents the sky for stoichiometric(al) combustion Throughput represents when λ=2 and provides twice of air mass flow and be used for stoichiometric(al) combustion, and impurity content will be given in the form of fuel equivalent Go out, the impurity in fuel is individually added into the form of equivalent；It is pressure-dependent by simulating the corrosion product dew point for calculating and generating Trendline, it is shown that there are the regions of heat erosion risk；
    Step 4: by analyzing influence of the major impurity changes of contents to dew point curve, main affecting factors are confirmed, and then complete In H2To the assessment of turbine blade of gas turbine heat erosion degree in the case of S is exceeded；Dew point will be increased as pressure increases, this More positions will be caused to face heat erosion risk, therefore analyzed respectively under the conditions of different pressures, sulfur content changes to corruption The affecting laws and chlorine metal that the affecting laws of erosion product dew point variation, alkali metal content variation change corrosion product dew point contain The affecting laws that amount variation changes corrosion product dew point.
CN201810470935.4A 2018-02-08 2018-05-17 Assess the method influenced on turbo blade heat erosion when hydrogen sulfide is exceeded in fuel gas Pending CN108647459A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1094122A (en) * 1992-12-02 1994-10-26 斯坦工业公司 Be mainly used in the device that reclaims the method for heat in the combined cycle and implement this method
WO2011004425A1 (en) * 2009-07-07 2011-01-13 株式会社日立製作所 Operation control method for gas turbine and operation controller for gas turbine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1094122A (en) * 1992-12-02 1994-10-26 斯坦工业公司 Be mainly used in the device that reclaims the method for heat in the combined cycle and implement this method
WO2011004425A1 (en) * 2009-07-07 2011-01-13 株式会社日立製作所 Operation control method for gas turbine and operation controller for gas turbine
CN102472170A (en) * 2009-07-07 2012-05-23 株式会社日立制作所 Operation control method for gas turbine and operation controller for gas turbine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
BETTINA BORDENET: "High Temperature Corrosion in Gas Turbines: Thermodynamic Modelling and Experimental Results", 《PITTSBURGH: UNIVERSITY OF PITTSBURGH》 *

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