CN109030326A - A method of measurement condensing heat exchanger low-temperature corrosion protection ability and corrosion rate - Google Patents
A method of measurement condensing heat exchanger low-temperature corrosion protection ability and corrosion rate Download PDFInfo
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Abstract
The invention discloses a kind of methods for measuring condensing heat exchanger low-temperature corrosion protection ability and corrosion rate, and wherein the measurement method of low-temperature corrosion protection ability is the following steps are included: Step 1: collect the condensate liquid being discharged in heat exchanger；Step 2: measuring the pH value of the condensate liquid.For the measurement method of corrosion rate, comprising the following steps: Step 1: the condensing liquid quantity collected in the measuring unit time；Step 2: using icp ms in condensate liquid sour component and metal component content measure, then statistics calculating is carried out to the heat exchanger condensation portion heat exchange area；Step 3: above-mentioned parameter is substituted into formula, corrosion rate is calculated.Simple using this method measurement parameter, process is easy to operate, and evaluation index is objective, can efficiently solve heavy workload present in the test methods such as experiment test, material immersion, simplation verification, the high problem of measurement difficulty.
Description
Technical field
The present invention relates to the methods of low-temperature corrosion protection ability and corrosion rate, in particular to a kind of in condensing heat exchanger
The method of flue gas low-temperature corrosive power and corrosion rate prediction.
Background technique
Condensing heat exchanger is widely used in gas heater, Industrial Boiler, economizer as a high-efficiency heat exchanger equipment
In the equipment such as air preheater.Contain vapor and SO in the flue gas formed due to fuel combustionXWith the sour gas such as NOx,
When the wall surface temperature that exchanges heat is lower than the condensation temperature of the sour gas, vapor and acid vapors can be in conjunction with the acid condensate liquids of generation
It is attached on the heat exchange wall surface of heat exchanger, heat exchanging wall face causes to corrode.This aspect will affect the new property of heat exchange of heat exchanger
Can, meeting heat exchanging device is damaged using safe and service life when serious.All high-performance heat exchanger is being greatly developed in the whole world
Under the technical background utilized with low-temperature flue gas waste heat, deep exploitation fume afterheat will make influence caused by above-mentioned low-temperature corrosion
It is more prominent and sharp.
Currently, being directed to the research method of flue gas low-temperature corrosive power and corrosion rate, mainly there are experiment test, material leaching
Bubble, simplation verification etc..Wherein experimental test procedures, test effect is the truest, but the experimentation period is longer, experimental implementation compared with
For complexity, extent of corrosion and area measurement especially for closed heat exchanger heat exchange wall surface are even more to be difficult to carry out.Test material
Expect infusion method, although easy to operate, a situation arises differ farther out with operating condition locating for real exchanger for corrosion, will lead to and tests survey
Test result and reality error are larger.And simplation verification method of testing can be very good the factor of control corrosion rate generation, such as flue gas
Composition, flue-gas temperature, flow velocity, heat exchange wall surface temperature change of middle acid vapors etc., the influence of heat exchanging device heat exchange wall surface.But mesh
Before until it is also less about the case using analog detection method research low-temperature corrosion, and about above-mentioned factor heat exchanging wall surface
Corrosion principle also utilizes empirical equation mostly, is unable to satisfy actual test required precision.Therefore for condensing heat exchanger
In the research process of low-temperature corrosion phenomenon, needing one kind can be with precise measurement and prediction low-temperature flue gas condensate corrosion ability and rate
Method.
Summary of the invention
It is an object of the invention to overcome the shortcomings of prior art, provide a kind of for flue gas low-temperature in condensing heat exchanger
The method of corrosive power and corrosion rate prediction, this method not only can be cold for judging by the measurement of the pH to condensate liquid
The power of corrosive power when solidifying formula heat exchanger inner cryogenic corrosion phenomenon occurs；It can also be according to the production of unit time inner condensat liquid
Raw amount and property, heat exchanging device inner cryogenic corrosion rate are measured.
In order to achieve the above object, the technical solution adopted by the present invention is that:
A kind of method for measuring condensing heat exchanger low-temperature corrosion protection ability and corrosion rate of the present invention, including heat exchanger low temperature
Anti-corrosion ability measurement method and heat exchanger corrosion rate measurement method；
The heat exchanger low-temperature corrosion protection ability measurement method, comprising the following steps:
The condensate liquid being discharged inside heat exchanger is collected, the pH value of the condensate liquid is then tested, if condensate liquid is acid solution
And pH value is larger or solution is neutral solution, then corrosion phenomenon occurs for heat exchanger wall surface more serious；If condensate liquid is acidity
Solution and pH value is smaller, then corrosion phenomenon occurs for heat exchanger wall surface lighter；
The heat exchanger corrosion rate measurement method, comprising the following steps:
(1) amount for the condensate liquid being discharged in the measuring unit time from heat exchanger condensation segment；
(2) using icp ms in the condensate liquid being collected into the unit time sour component and
The content of metal component measures, the amount of metal that the amount and heat exchanger wall surface of the metal component obtained by measurement are corroded
It is identical；The heat exchange area that part occurs to the heat exchanger inside smoke condensation simultaneously carries out statistics calculating；
(3) it is calculated using the following equation the corrosion rate of the heat exchanger:
Wherein NfFor the corrosion rate of heat exchanger condensation portion wall surface, unit is mol/ (sm2)；V is to receive in the unit time
Collect the volume of obtained condensate liquid, unit m3；Mass concentration of the C for institute's eroded elements in collected condensate liquid, unit g/
m3；A is the heat exchanger wall surface area that condensation occurs in heat exchanger, unit m2；T is acquisition time length, unit s；M
For the molal weight for the element that is corroded, unit g/mol.
The beneficial effect of the method for the present invention is: this method needs measurement parameter simple, and measurement process is easy to operate, evaluation index
It is objective.And this method efficiently solves workload present in the test methods such as experiment test, material immersion, simplation verification
Greatly, the high problem of measurement difficulty.
Detailed description of the invention
Fig. 1 is the relational graph between low-temperature corrosion protection ability and anti-corrosion rate and heat exchange wall surface temperature；
Fig. 2 is heat exchanger wall-surface condensation schematic diagram.
Specific embodiment
The present invention will be described in detail in the following with reference to the drawings and specific embodiments.
From figure 1 it appears that the corrosion rate of heat exchanger wall surface with heat exchange wall surface temperature it is related, and with condensed water
PH value shows negative correlativing relation.For current natural gas, wherein H2S content is about 8ppm, in normal combustion operating condition, flue gas
Condensation temperature is related to the excess air coefficient of burning and combustion conditions, when excess air coefficient is 1.0, shape after burning
Dew-point temperature at flue gas is 57 DEG C.When wall surface temperature is higher than this number, condensation does not occur for the vapor in flue gas, just
Condensed water attachment will not be formed in wall surface, the low-temperature corrosion phenomenon of wall surface will not be caused.And with the decline of wall surface temperature, when
When temperature is lower than condensation temperature [t], the vapor in flue gas starts to condense, and absorbs acid vapors in flue gas, is formed acid molten
Liquid.Due to the condensation of vapor at this time, cause the decline of steam partial pressure in flue gas, in flue gas the meltage of acid vapor also compared with
Few, the solution ph formed at this time is higher.With the reduction of heat exchange wall surface temperature, the condensing rate of vapor is accelerated, condensed water
Amount increases, and the pH value of condensed water also declines therewith.When saturated vapour pressure under vapor is condensed to the pressure, exchange heat wall surface
Corrosion rate reaches local maxima, and the pH value of condensed water also reaches Local Minimum at this time.It is cold when wall surface temperature further declines
Condensate flow increases, steam partial pressure decline, and the partial pressure of sour gas increases, cause the meltage of sour gas not with
Increase, the pH value of condensate liquid reaches local maxima at this time.With the dew point temperature for continuing to drop to acid vapors of wall surface temperature
Degree, a large amount of acid vapors also start to condense at this time, in condensed water other than partly soluble acid ion, increase a large amount of
Acid solution is condensed, the pH value of condensate liquid also can sharply decline.
Under condensing heat exchanger normal operation, the condensed water being discharged inside heat exchanger is collected, and test and be somebody's turn to do
The pH value of condensing soln, the numerical value can be used for characterizing the index of the low-temperature corrosion protection ability of heat exchanger.When pH value is larger, close to numerical value
When 7, illustrate that acid solution composition is less from the condensate liquid that heat exchanger internal condensation section is discharged, and neutral salting liquid ingredient compared with
More, this further extrapolates the part acid solution and stronger electrochemical corrosion reaction occurs in heat exchanger wall surface material, largely
Acid solution is reacted with the metallic element in heat exchanger wall surface material, this just makes the pH that the condensate liquid of heat exchanger is discharged
It is worth larger.Similarly, when the pH value of test gained condensate liquid is smaller, illustrate the acid solution of condensation not inside heat exchanger
Violent electrochemical method occurs for the metal material of condensation segment and heat exchanger, this is moved out a large amount of acid ion to change
Hot device, into test sample.Therefore the low of characterization condensing heat exchanger can be very good by the condensate liquid that test is collected into
Warm anti-corrosion ability.
Based on principles above, the side of a kind of measurement condensing heat exchanger low-temperature corrosion protection ability and corrosion rate of the invention
Method, including heat exchanger low-temperature corrosion protection ability measurement method and heat exchanger corrosion rate measurement method；
The heat exchanger low-temperature corrosion protection ability measurement method, comprising the following steps:
The condensate liquid being discharged inside heat exchanger is collected, the pH value of the condensate liquid is then tested, if condensate liquid is acid solution
And pH value is larger or solution is neutral solution, then heat exchanger wall surface generation corrosion phenomenon is more serious, and pH value generally exists at this time
Between 5-7；If condensate liquid is acid solution and pH value is smaller, heat exchanger wall surface generation corrosion phenomenon is lighter, at this time pH value one
As between 3-5；
If heat exchanger wall surface occurs, corrosion phenomenon is more serious, illustrates that the hydrogen ion in condensate liquid occurs in heat exchanger wall surface
Chemical reaction causes hydrogen ion content in the liquid of discharge heat exchanger just to tail off, and the condensate liquid pH value being collected at this time also can
It is higher；If heat exchanger wall surface, there is no corrosion phenomenons, and the acid condensate liquid that generation is condensed in condensate liquid can be expelled directly out
Heat exchanger, the condensate liquid pH value being collected at this time can be smaller.By above-mentioned analysis, herein can by the pH value to condensate liquid into
Row test, the pH that test is obtained is as the low-temperature corrosion protection capacity index for judging the condensing heat exchanger.
The heat exchanger corrosion rate measurement method, comprising the following steps:
(1) amount for the condensate liquid being discharged in the measuring unit time from heat exchanger condensation segment；
(2) using icp ms (ICP-MS) to the acid in the condensate liquid being collected into the unit time
The content of ingredient and metal component measures, and amount and the heat exchanger wall surface of the metal component obtained by measurement are corroded
Amount of metal it is identical.The heat exchange area that part occurs to the heat exchanger inside smoke condensation simultaneously carries out statistics calculating, can
To be solved using directly measurement, wherein area can be obtained directly by the length of erosional surface and wide quadrature at the smooth wall surface that exchanges heat,
And fin area can be solved to obtain by the area to cylindrical outer surface, entirely be condensed finally by adduction
Partial heat exchange area.And as the heat exchanger have Related Mathematical Models, then can also directly adopt condensing heat-exchange area into
Row calculates.The two methods are the prior art.
(3) it is calculated using the following equation the corrosion rate of the heat exchanger:
Wherein NfFor the corrosion rate of heat exchanger condensation portion wall surface, unit is mol/ (sm2)；V is to receive in the unit time
Collect the volume of obtained condensate liquid, unit m3；Mass concentration of the C for institute's eroded elements in collected condensate liquid, unit g/
m3；A is the heat exchanger wall surface area that condensation occurs in heat exchanger, unit m2；T is acquisition time length, unit s；M
For the molal weight for the element that is corroded, unit g/mol.
Embodiment 1
Wherein the material of condensing heat exchanger be casting silico-aluminum, the material of the casting sial heat exchanger after spectrum analysis,
Learning that wherein Al content is 87.21%, Si content is 11.7%, other are Fe, the elements such as Cu, Mn.
When flue gas flows through the heat exchange wall surface of heat exchanger, temperature TfFlue gas and fin and heat exchange wall surface exchange heat, it is first
First a temperature boundary layer can be will form at the fin of heat exchange wall surface, when flue gas is contacted with wall surface, flue-gas temperature drops to
Identical as wall surface temperature, i.e., temperature is t1, and in wall peripheral, flue-gas temperature gradually rises, until maximum value t2.It is assumed that
Temperature t1Greater than the condensation temperature [t] of flue gas, that is, illustrate that the temperature on fin surface is all larger than the dew-point temperature of flue gas, flue gas everywhere
In vapor condensation will not then occur, also there will be no the generations of condensed water.But with cold water temperature TwReduction, t1
Temperature also can be with declining, if temperature t at this time1Value be less than flue gas dew-point temperature [t], then the surface of fin then
It will form a humidity province, the temperature on the area inner rib plate surface is respectively less than dew-point temperature [t], and specific region can be found in Fig. 1
Condensation film region.Condensation can occur in this area for the vapor in flue gas at this time, this region can be defined as " flue gas
Condensing zone ".It can find t1It is worth smaller, the area in " flue gas condensing area " is bigger, and the condensation water quantity of generation also can be more.And it is same with this
Shi Wendu TwWater entered inside heat exchanger by the direction contrary with flow of flue gas and exchange heat.
Contain a large amount of acid solution in the moisture film that " flue gas condensing area " is formed, pH value is less than 7, due to the casting sial
Heat exchanger materials contain multiple element, and the active characteristic between each element is different, and the Al element in such heat exchanger materials is sun
Pole, other elements are cathode, and due to being in close contact between Al element and other elements, are just formed between them numerous micro-
Small electrochemical corrosion circuit, when the material and above-mentioned acidic leach of casting sial surface contact, it may occur that galvanic interaction, material
More active metal can lose electronics and be oxidized in material, so that electrochemical corrosion occur.The circuit master of the electrochemical corrosion
It to include cathode, four anode, electrolyte solution and external loop parts.The chemical reaction specifically occurred is as follows:
Al-3e-→Al3+
O2(g)+2H2O+4e-→4OH-(aq)
Al3++3OH-→Al(OH)3
2Al(OH)3→Al2O3+3H2O
Al ion in casting sial heat exchanger wall surface material is because electrochemical reaction is oxidized to Al3+Ion, and be dissolved in
O in water2And H2O generates OH after obtaining electronics-Ion, wherein OH-Ion with the Al on heat exchanger wall surface3+Ion side
After formula reaction, Al (OH) can be formed in heat exchanger wall surface3.The Al (OH) later3It can be oxidized once again and be generated as Al2O3And H2O,
Middle Al2O3One layer of fine and close oxidation film can be formed in heat exchanger wall surface, further corrode effect with prevent acid solution.
Heat exchanger low-temperature corrosion protection ability measurement method is carried out using the method for the present invention, comprising the following steps:
(1) condensate liquid being discharged inside heat exchanger is collected, the pH value of the condensate liquid is then tested.
(2) if condensate liquid pH value is between 5~7 at this time, determine the low temperature of flue gas in condensing heat exchanger at this time
Corrosive power is stronger, also can determine that the low-temperature corrosion protection erosion ability of condensing heat exchanger wall surface at this time is weaker；If condensate liquid at this time
PH value between 3~5, then determine that the low-temperature corrosion ability of flue gas in condensing heat exchanger at this time is weaker, also can determine that this
When condensing heat exchanger wall surface low-temperature corrosion protection erosion ability it is stronger.
The condensate liquid pH value that sial condensing heat exchanger is cast described in this patent is obtained using the above method and step measurement
It is 4, illustrates that the low-temperature corrosion ability for casting flue gas in sial condensing heat exchanger at this time is weaker, and the low-temperature corrosion protection of wall surface loses ability
It is relatively strong.
After testing test, to equipment overhaul, find do not occur on heat exchange fin and wall surface in heat exchanger
Phenomena such as corrosion pit and spot, illustrates that the material heat exchanger has stronger low-temperature corrosion ability, while it is low also to demonstrate this
The reliability of warm anti-corrosion capability measurement method.
The measurement of heat exchanger corrosion rate is carried out using the method for the present invention, comprising the following steps:
(1) amount for the condensate liquid being discharged in the measuring unit time from heat exchanger condensation segment；
(2) using icp ms (ICP-MS) to the acid in the condensate liquid being collected into the unit time
The content of ingredient and metal component measures.
(3) heat exchange area that part occurs to the heat exchanger inside smoke condensation counts.
(4) it is calculated by using the following formula the corrosion rate of the heat exchanger:
Using the above method and step, being tested to obtain: V to casting sial condensing heat exchanger in the present embodiment is
0.03m3/h；C is 11.8g/m3；A is 2.1m2；T is 1 hour, 3600s；M is Al, molal weight 27g/mol.Calculation formula
Obtain the corrosion rate N of this casting sial heat exchangerfIt is 1.7 × 10-6mol/(s·m2)。
It is found by the concrete operations of the implementation case, this method is for low-temperature corrosion protection ability and anticorrosion rate
It in measurement, needs measurement parameter simple and easily realizes, measurement process is succinct and easily grasps, and evaluation index is objective.And this method has
Effect solves experiment test, material immersion, heavy workload present in the test methods such as simplation verification, measures that difficulty is high to ask
Topic.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all principle of the invention it
Interior, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.
Claims (1)
1. a kind of method for measuring condensing heat exchanger low-temperature corrosion protection ability and corrosion rate, it is characterised in that: including heat exchanger
Low-temperature corrosion protection ability measurement method and heat exchanger corrosion rate measurement method；
The heat exchanger low-temperature corrosion protection ability measurement method, comprising the following steps:
The condensate liquid being discharged inside heat exchanger is collected, the pH value of the condensate liquid is then tested, if condensate liquid is acid solution and pH
Being worth larger or solution is neutral solution, then corrosion phenomenon occurs for heat exchanger wall surface more serious；If condensate liquid is acid solution
And pH value is smaller, then corrosion phenomenon occurs for heat exchanger wall surface lighter；
The heat exchanger corrosion rate measurement method, comprising the following steps:
(1) amount for the condensate liquid being discharged in the measuring unit time from heat exchanger condensation segment；
(2) using icp ms to the sour component and metal in the condensate liquid being collected into the unit time
The content of ingredient measures, the amount of metal phase that the amount of the metal component obtained by measurement is corroded with heat exchanger wall surface
Together；The heat exchange area that part occurs to the heat exchanger inside smoke condensation simultaneously carries out statistics calculating；
(3) it is calculated using the following equation the corrosion rate of the heat exchanger:
Wherein NfFor the corrosion rate of heat exchanger condensation portion wall surface, unit is mol/ (sm2)；V is to collect in the unit time
The volume of the condensate liquid arrived, unit m3；Mass concentration of the C for institute's eroded elements in collected condensate liquid, unit g/m3；A is
The heat exchanger wall surface area that condensation occurs in heat exchanger, unit m2；T is acquisition time length, unit s；M is rotten
Lose the molal weight of element, unit g/mol.
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