WO2010078712A1

WO2010078712A1 - Method and system for on-line determining corrosive acid radical anion content in phosphate boiler water of drum boiler unit of power plant

Info

Publication number: WO2010078712A1
Application number: PCT/CN2009/001551
Authority: WO
Inventors: 李长鸣; 何俊峰
Original assignee: 河南电力试验研究院
Priority date: 2008-12-29
Filing date: 2009-12-24
Publication date: 2010-07-15
Also published as: CN101446564B; CN101446564A

Abstract

Disclosed are a method and a system for on-line determining corrosive acid radical anion content in phosphate boiler water of drum boiler unit of power plant. Said method comprises the following steps: determining phosphate content in boiler water, determining hydrogen electrical conductivity of boiler water after passing cation exchange column, and determining corrosive acid radical anion content based on the phosphate content and the hydrogen electrical conductivity.

Description

The present invention claims priority to Chinese Patent Application No. 2008 1018 766 9.0 filed on Dec. 29, 2008, the entire disclosure of which is incorporated herein by reference. Technical field

The invention relates to a steam water monitoring technology for a power plant, in particular to a method for determining a corrosive acid anion content in a phosphate furnace water of a high-parameter steam drum furnace of a power plant. The invention also relates to a system for determining the content of corrosive acid radical anions in a phosphate furnace water of a high-parameter steam drum furnace of a power plant. Background technique

In the furnace water treatment of steam boiler units in thermal power plants, phosphate treatment is the most classic and common method of furnace water treatment. In the present invention, the furnace water of a steam-fired boiler of a thermal power plant adopting a solution of a solution of a solution is referred to as "phosphate furnace water". It is necessary to timely measure and control the corrosive acid anions as impurities in the phosphate furnace water to ensure the safe and economic operation of the boiler and the unit.

Under normal conditions, the corrosive impurity ions in the phosphate furnace water are mainly corrosive acid anions present. These "corrosive acid anions" which are generally considered as impurities include chloride ions and sulfate ions, and in general, chloride ions are first. The higher the unit parameters, the stricter the requirements for their content control, and the more difficult the analysis. The current methods for the analysis of corrosive acid radical anions in furnace water are mainly manual titration analysis or spectrophotometry for chloride ions. The manual titration analysis method has long been extended in the power industry, which is simple and easy, but the main disadvantage is that the lower limit of determination is too high, both above lmg/L. For high-parameter (subcritical) steam drum furnace units, in some phosphate treatment furnace water, the chloride ion control index is on the order of 10 ² ug/L, which is lower than the lower limit of the conventional manual titration analysis. Manual titration analysis has been difficult to accurately determine the chloride ion Content; For spectrophotometry, because the analysis process is too complicated, no one wants to do it, and the scope is narrow. For containing

Phosphate furnace water of the order of corrosive acid anion, within the range of such common impurity content, the above existing methods cannot even form a cover. In addition, manual analysis operations do not allow for timely monitoring of sudden increases in corrosive anions that may occur. For the combined monitoring of chloride and sulfate ions, the common method is ion chromatography. The sensitivity of this method is higher than that of manual operation and can be accurately determined to ^ / L. However, the disadvantage of ion chromatography is that it cannot be used for online monitoring. And ion chromatography uses large instruments, which have high operational requirements and are not available in general power plants. The fast-developing high-parameter (subcritical) steam drum furnace unit's phosphate treatment method, especially the low-phosphate treatment method, has stricter requirements on the control of corrosive acid radical anion content, and there is an urgent need for a phosphate furnace water that can be monitored in time. Method to satisfy

The range of requirements for continuous determination of corrosive acid anions.

The hydrogen ion conductivity measurement method is a classical physical and chemical method for determining the total amount of acid anions in the steam water sample of power plants. The measuring principle is that the soda water sample passes through a fully regenerated hydrogen-type strong acid type cation exchange resin column, and the cations in the water sample are all converted into hydrogen ions, and the acid anions are all passed as they are; at the outlet of the cation exchange column, in the water sample component The corresponding acidity of the acid-containing anion is converted into its corresponding acid. The corresponding conductivity of the post-column water sample of the hydrogen-type strong acid type cation exchange column is called hydrogen ion conductivity, referred to as hydrogen conductivity or hydrogen conduction, and is uniformly abbreviated as CC:. Hydrogen conductivity can be measured with an accuracy of 0.01 pS/cm, which accurately shows the change in the concentration of acid anions in several micrograms per liter of water. Hydrogen ion conductivity measurement has been successfully used to continuously monitor the total amount of corrosive acid anions in sodium hydroxide treated steam drum furnace water, and to mass concentration (p _g /L) or hydrogen ion conductivity (pS / cm) The form indicates that this method has long been internationally recognized and is widely adopted and incorporated into relevant standards. According to the physical and chemical principle of the hydrogen ion conductivity measurement method, it has significant advantages in the determination of trace acid anions: The electrode response is sensitive and fast, and the instrument is simple and reliable, which is convenient for on-line measurement. The principle and detailed operation of the method for measuring hydrogen ion conductivity can be found in relevant standards. For example, see "People's Republic of China Power Industry Standard, DL/T 502.29-2006, Determination of Hydrogen Conductivity.

However, in the furnace water of the phosphate treatment unit of the steam drum furnace unit, due to the presence of phosphate and the contribution of phosphate to hydrogen conductivity, it is not possible to directly use hydrogen conductivity before deducting the contribution or influence of phosphate on hydrogen conductivity. Characterizes the corrosive acid radical anion content of the furnace water as an impurity. Therefore, in January 2004, the American Academy of Electric Power (EPRI) recommended in its latest guidelines for solid caustic treatment of steam drum furnaces that the corrosive acid anion content of furnace water and the conductivity of hydrogen and conductivity of furnace water were summarized. It is used to monitor the changes of boiler water, but so far there have been no reports of relevant research progress at home and abroad.

To this end, an efficient, simple, easy, timely, sensitive and online method for monitoring the content of corrosive acid anions in the phosphate furnace water of a high-parameter steam drum furnace of a power plant is provided, and a method for determining the same is provided. The system is still an urgent problem to be solved by those skilled in the art. Summary of invention

To achieve the objectives of the present invention, the present invention provides the following items:

A method for determining the content of corrosive acid anions in a phosphate furnace water of a high-parameter steam drum furnace of a power plant, the method comprising determining the phosphate content in the furnace water (C _P04 ) and the hydrogen conductance of the furnace water after passing through the cation exchange column The rate (CC furnace water) step, and the step of determining the content of corrosive acid radical anion based on the measured phosphate content (C _P04 ) and hydrogen conductivity (CC).

2. According to the method of item 1, it is applicable to the high-parameter unit phosphate furnace water of the power plant,

The amount of corrosive acid radical anion in the order of magnitude is effectively determined.

3. The method according to item 1, wherein the phosphate content in the furnace water is determined by a colorimetric method, a spectrophotometric method, or an on-line phosphorus table measurement method.

4. The method according to item 1, wherein the corrosive acid is an anion selected from one or more of a chloride ion, a sulfate ion, a carbonate ion, and an acetate ion.

5. The method according to any one of items 1 to 4, wherein the corrosive acid anion The content is characterized by the hydrogen conductivity of the corrosive acid anion (ie, CC humate anion), wherein the CC humic acid is hydrogen from the furnace water hydrogen conductivity (CC furnace water) and the phosphate in the furnace water. The difference in conductivity (CC _P04 ) is determined.

6. The method according to any one of items 1 to 4, wherein the content of the corrosive acid anion is characterized by a mass concentration (C) of the corrosive acid anion; the method comprising determining a corrosive acid radical having the highest content in the furnace water; a step of anion as the first acid 3⁄41 anion, and a step of determining the mass concentration (C) of the corrosive acid anion according to the first acid anion; the first acid anion is selected from the group consisting of chloride ion, sulfate ion, and carbonic acid Only cesium ions, or acetate ions.

7. The method according to item 6, wherein the method for determining the phosphate furnace water of the high-parameter steam drum furnace of the power plant, the applicable first acid anion content range is lO^lO^g/L; preferably, the first The monoacid anion is a chloride ion.

The method according to any one of items 1 to 4, wherein the content of the corrosive acid anion is characterized by a mass concentration of the first acid anion (i.e., d acid group, wherein the C acid anion is hydrogen by furnace water The conductivity (CC furnace water) is determined by the difference between the hydrogen conductivity (CC _P04 ) of the phosphate in the furnace water and the conversion factor of the first acid anion; the method is suitable for determining the amount of lO ^ lO ^ g L The first acid anion power plant high-parameter steam drum furnace phosphate furnace water; preferably, the first acid anion is chloride ion.

9. A system for determining a method for determining a corrosive acid anion content in a phosphate furnace water of a high-parameter steam drum furnace of a power plant according to item 1, comprising a furnace water phosphate content determining unit and a furnace water hydrogen conductivity measuring unit And introducing the sample of the furnace 7j into the piping of the two measuring units, respectively.

10. The system of item 9, wherein the furnace water hydrogen conductivity measuring unit comprises, in order of flow direction of the furnace water sample, a cation exchange column, an electrode cup, a conductivity electrode in contact with the furnace water sample in the electrode cup, and The conductivity electrode is electrically connected to the conductivity meter.

11. The system according to item 9, wherein the furnace water phosphate content determining unit It is an online phosphor meter, colorimeter or spectrophotometer.

12. The system according to any one of items 9 to 11, which further comprises a calculation unit for processing data measured by the furnace water phosphate content measuring unit and the furnace water hydrogen conductivity measuring unit.

13. The system according to item 12, wherein the calculating unit is selected from the group consisting of: a single-chip microcomputer or a centralized sampling computer electrically connected to the furnace 7 phosphate content measuring unit and the furnace water hydrogen conductivity measuring unit, physically independent of each other a computer, a built-in single chip integrated with the conductivity meter and electrically connected to the conductivity meter and the furnace water content measuring unit, and integrated with the furnace water phosphate content measuring unit and the conductivity meter and electrically connected thereto Built-in microcontroller with sexual connection. Detailed description of the invention

The problem to be solved by the present invention is to provide a method for conveniently monitoring the content of corrosive acid anion in the phosphate furnace water of a high-parameter steam drum furnace of a power plant, and another problem to be solved by the present invention is to provide a method for providing A system for determining the content of corrosive acid anions in phosphate furnace water of a high-parameter steam drum furnace of a power plant.

To this end, the first aspect of the present invention provides a method for determining a corrosive acid anion content in a phosphate furnace water of a high-parameter steam drum furnace of a power plant, the method comprising separately determining a phosphate content (C _P04 ) in the furnace water and passing the furnace water The step of hydrogen conductivity (CC furnace water) after the cation exchange column, and the step of determining the content of corrosive acid anion based on the measured phosphate content (C _P04 ) and hydrogen conductivity (CC furnace water).

In one embodiment of the method of the present invention, there is provided a method for online determination of a corrosive acid radical anion content in a phosphate furnace water of a high parameter steam drum furnace of a power plant, the method comprising separately determining a phosphate content (C _P04 ) in the furnace water and The step of hydrogen conductivity (CC furnace water) after passing the furnace water through the cation exchange column, and the step of determining the content of corrosive acid anions based on the measured phosphate content (C _P04 ) and the furnace water hydrogen conductivity (CC).

In the method of the present invention, the content of the corrosive acid anion may be guided by hydrogen Characterized by rate (cc) or mass concentration (c), any other parameter that can be used to characterize the content of corrosive acid anion, such as (ppb = ug / kg or ppm = mg / kg, etc.) can also be employed.

The term "acid anion" as used in the present invention generally refers to all acid anions including phosphate ions. The term "corrosive acid anion" as used in the present invention generally refers to all acid anions in the furnace water which may corrode the steam drum furnace unit in addition to the phosphate ions, including but not limited to one selected from the group consisting of or A variety of acid anions: chloride, sulfate, carbonate, acetate, these corrosive acid anions are usually present as impurity ions, in practice, they are required to control the safe operation of the drum furnace unit Within the scope of the standard license. The specific standard values of corrosive acid anion content vary depending on boiler parameters and specific phosphate treatment methods. For subcritical units, on the order of 10 ² -10 _g /L (see the People's Republic of China Power Industry Standard DL/T 805.2 - 2004) Steam-water chemical guides for thermal power plants - Part 2: Boiler furnaces.

In one embodiment of the process of the present invention, the method is effective for determining the amount of corrosive acid anion in the phosphate furnace water in the range of 10 O ^ g / L, which is effective for both normal and abnormal operation of the furnace water. In other words, the method of the present invention is suitable for the determination of phosphate furnace water in a high-profile steam drum furnace of a power plant containing a corrosive acid anion of the order of lO^lO^L.

In an embodiment of the method of the present invention, wherein the phosphate content in the furnace water can be determined by various methods, including but not limited to: colorimetry, spectrophotometry (such as the People's Republic of China standard GB/ T6913-93 "Determination of Phosphate for Analysis of Boiler Water and Cooling Water", often used for colorimetric or spectrophotometric analysis), on-line phosphorus spectrometry (see: "Power Plant Chemical Instruments" Chapter 4, Fifth Section of the comfort of the co-edited China Electric Power Press, the second edition of October 1998; the People's Republic of China power industry standard DL / T677-1999 "power plant online chemical instrument inspection procedures" and so on. In one embodiment of the process of the invention, the phosphate content of the furnace water is determined using an in-line phosphorus spectrometry. In one embodiment of the process of the invention, wherein the cation exchange column is a hydrogen type strong acid type cation exchange column. In another embodiment, the cations in the furnace water are all converted to hydrogen ions as they pass through the cation exchange column, and the anions in the furnace water pass through the cation exchange column as they are. In yet another embodiment, after passing through the cation exchange column, the acid anions in the furnace water are converted to their corresponding acids.

In one embodiment of the method of the present invention, wherein the acid anion comprises a phosphate ion and one or more ions selected from the group consisting of chloride ion, sulfate ion, carbonate ion, acetate ion. In another embodiment of the method of the invention, the acid anion comprises a phosphate ion and one or more ions selected from the group consisting of chloride ions, sulfate ions.

In one embodiment of the method of the present invention, the corrosive acid moon ions include, but are not limited to, chloride ions, sulfate ions, carbonate ions, acetate ions. In another embodiment of the method of the invention, the corrosive acid anion described therein includes, but is not limited to: chloride ions, sulfate ions.

In the present invention, the chemical ionization equation of the corresponding acid of each of the acid anions can be determined according to the principle of chemical ionization. In the present invention, the corresponding acids of the phosphate ions, chloride ions, and sulfate ions are ionized in the following manner:

H ₃ P0 ₄ →H+ + H ₂ P0 ₄ ,

HC1→H ⁺ + C1 ,

H ₂ S0 ₄ → 2H ⁺ + S0 ₄ ² .

In an embodiment of the method of the present invention, wherein the furnace water hydrogen conductivity (CC is measured at or near a standard temperature of the hydrogen conductivity measuring method. For example, in the "Power Industry Standard of the People's Republic of China" , DL/T 502.29-2006, Determination of Hydrogen Conductivity" is carried out at the temperature specified, in particular at a standard temperature of 25 ° C. In one embodiment of the process of the invention, in the case of a power plant The sampling, treatment and subsequent determination, calculation and/or conversion of the water sample of the boiler drum water of the parameter steam drum furnace are preferably in the corresponding industry standards. The standard temperature (25 ° C) is at or near the standard temperature. For example, the sampling operation of the water sample can be based on the "People's Republic of China Power Industry Standard, DL/T 457-1991, Water and Gas Sampling Device". It is stipulated that the temperature of the outlet 7 is controlled by a thermostat to be 25 ± 1. C. Those skilled in the art understand that in the event that the actual temperature deviates from the standard temperature, the temperature can be corrected to perform measurements, calculations, and/or conversions at standard temperatures.

In one embodiment of the method of the present invention, wherein the content of the corrosive acid anion may be characterized by a hydrogen conductivity of the corrosive acid anion (ie, a CC acid sig), wherein the CC acid radical is The difference between the hydrogen conductivity of the furnace water (CC furnace water) and the hydrogen conductivity of the phosphate in the furnace water (CC _P04 ) is determined. In the present invention, the term appearing as a lower corner of a certain parameter means the parameter defined by the lower-angled term, such as the above-mentioned "CC corrosive acid anion," and "CC" respectively represent all corrosive acids. The value of the hydrogen conductivity contributed by the anion and the value of the hydrogen conductivity contributed by all ions in the furnace water.

The calculation used to determine CC acid radicals is:

CC Corrosive Acid Anion ⁼ C!C! Furnace Water - CC! PO4,

among them:

Specifically, in the method of the present invention, the phosphate content of the furnace water c _{P04 is} first determined by a phosphate content measurement method, and the hydrogen conductivity CC _{P04 of the} phosphate in the furnace water is calculated based on the measured content. The hydrogen conductivity CC _P04 of the phosphate in the furnace water is calculated as: CC _P04 =C _P04 xk _P04 (where k _P04 is the conversion factor, the value depends on the unit of CC _P04 and C _P04 . The unit of CC _P04 is usually take S / cm, the unit taken as C _P04 g / L, the k _P04 is 4.06xl0- ^3, if the fetch unit C _P04 mg / L, the k _P04 4.06). In the present invention, the term appearing as a lower corner of a certain parameter means the parameter defined by the lower horn term, for example, "C _P04 " above indicates the mass concentration of phosphate ions in the furnace water.

In an embodiment of the method of the present invention, wherein the content of the corrosive acid anion is further characterized by a mass concentration (C) of the corrosive acid anion, wherein The method includes the steps of determining that the acid salt having the highest content in the furnace water is also referred to as a first acid anion (from chloride ions, sulfate ions, carbonate ions, acetate ions), and determining the first acid anion according to the first acid anion The step of mass concentration (C) of corrosive acid anions. The term "first acid anion" as used in the present invention generally means an anion having the highest concentration among all acid anions other than phosphate ions in phosphate furnace water. In production practice, the first acid anion is usually chloride ion, which is corrosive to the steam drum furnace unit and requires monitoring according to standards.

The first acid anion in the sample to be tested 7j can be determined by methods well known to those skilled in the art, including but not limited to ion chromatography. In the general production practice, in the case of stable operation of the high-parameter steam drum furnace, the chloride ion content in the furnace water does not change the dominant position of the CC ^, «root" contribution ratio, so the above method (such as ion chromatography) The determination of the first acid anion can meet the required quantitative or semi-quantitative determination requirements, and does not require frequent calibration with ion chromatography. In one embodiment of the method of the invention, the first acid anion is a chloride ion. In another embodiment of the method of the present invention, wherein the first acid anion used to determine the mass concentration (C) of the corrosive acid strontium anion is present in the phosphate furnace water is

The first-acid anion of the power plant is a high-value steam drum furnace with phosphate furnace water. In another embodiment, the first acid anion is a chloride ion, and the common content of the chloride ion in the phosphate furnace water is

The order of magnitude, that is, the method of the present invention is applicable to the determination of phosphate furnace water in a high-parameter steam drum furnace of a power plant containing chlorine ions of the order of lO'-lO^g L.

In an embodiment of the process of the invention, the chloride ion content of the corrosive impurities in the furnace water is generally significantly higher than the sulfate ion content under high-parameter drum furnace conditions, and is generally much higher than corrosion other than phosphate ions. The content of acid chloride anions such as carbonate ions and acetate ions is dominant. It can be represented by chloride ion and the equivalent content of hydrochloric acid is used to calculate the approximate content.

In one embodiment of the process of the invention, in the case of a high parameter steam drum furnace, such as The chloride ion content of corrosive impurities in the boiler water is generally not significantly higher than the sulfate ion content in all levels, and can be based on the average content ratio of the chloride ion and sulfate ion in the furnace water (quantity concentration and limit equivalent). Correction of the ratio of conductance synthesis). The present invention suggests that when the contribution of the first acid anion to the CC corrosive acid anion is generally less than 80%, it should be corrected as follows, so that its influence can be ignored.

(1) First, according to the results of ion chromatography, the hydrogen conductivity of the first acid anion is calculated according to the formula (a). The first acid anion of the CC humic acid anion

C first acid anion ^x k first acid anion

GG first acid anion % ~ ― (a)

G first acid anion ^x k first acid anion + C second acid anion ^x k second acid anion is normally: CC first acid anion % ⁼ (Cci ^x kci) / (C _S0 ^x kso4 + Cci ^x kci )

(2) If the CC first acid anion % is generally low in each order, the average value (CC first acid anion)

< 80%, it is recommended to calculate the corrected hydrogen conductance of the first acid anion by the formula (b) CC first acid anion, calibration.

CC first acid anion, calibration one CC first acid anion % xCC corrosive acid anion

= cc first acid anion % x (CC furnace water - CC _P04 ) (b)

(3) Calculate the corrected mass concentration of the first acid anion according to formula (c) C First acid anion, school "»

C first acid anion, correction ⁼ CC first acid anion % ^X (CC furnace water - GGpo4) k first acid anion (c) ratio of chloride ion to sulfate, which can be periodically or not by a suitable method such as ion chromatography It is periodically measured for approximate calculation and correction; this approximation can fully meet the accuracy requirements of actual measurement and control of trace impurities in furnace water. In one embodiment of the method of the present invention, the content ratio of the chloride ion to the sulfate ion can be determined by, for example, but not limited to, the following methods: ion chromatography, spectrophotometry, and the like. In one embodiment of the method of the invention, the ratio of chloride ion to sulfate ion content is determined by ion chromatography. The above-mentioned "regular" or "irregular" determination of the ratio of chloride ion to sulfuric acid is determined according to the operating conditions of the equipment. For example, when the phosphate treatment furnace water runs smoothly and normally, the measurement interval can be longer to confirm Its change is within the allowable range; When the phosphate treatment furnace water is abnormal, the measurement must be increased as appropriate to diagnose the cause of the abnormality and eliminate it.

In one embodiment of the method of the present invention, wherein the content of the corrosive acid anion may also be characterized by a mass concentration of the first acid anion (ie, a C-acid group), wherein the C-acid radical _M ÷ is a furnace The water-hydrogen conductivity (CC is determined by the difference between the hydrogen conductivity of the phosphate in the furnace water (CC _P04 ) and the conversion factor of the first acid-based anion.

Specifically, in the method of the present invention, according to the difference between the hydrogen conductivity (CC) of the furnace water and the hydrogen conductivity CC _P04 of the phosphate in the furnace water, and using the corresponding acid of the first acid anion at a standard temperature ^ The limit equivalent conductance is a standard, and the content of the corrosive acid anion represented by the first acid anion is determined. Determine the force used for the C first acid group: C first acid anion = (CC furnace water - CCpo4) / k first acid anion. Of course, the difference in the hydrogen conductivity of the furnace water and the phosphate can also be used to characterize the corrosive acid anion content in the boiler water: CC first acid anion-CC furnace water-CC _P04 . In the above two calculations, the unit of CC first acid anion, CC and CC _P04 is usually S/cm.

In an embodiment of the method of the present invention, the common content of the first acid anion in the phosphate furnace water is of the order of 10 O ^ g / L, that is, the method of the invention is suitable for determining the concentration of lO ^ 10 ^ g The first acid anion of the power plant high-parameter steam drum furnace unit phosphate furnace water. In another embodiment of the method of the invention, the first acid anion is a chloride ion. In the case where the first acid anion is ci-, if its unit is mg/L, the shell, Jk first acid anion is 12.0; if its unit is g/L, then k the first acid anion is 0.012.

In one embodiment of the method of the present invention, after determining the phosphate content and the furnace water hydrogen conductivity, the resulting values of CC and C _P04 can be input into the calculation unit in a variety of ways, including Not limited to: manual input method, computer automatic centralized acquisition method, single-chip automatic acquisition method.

In an embodiment of the method of the present invention, the calculation of the corrosive acid anion of the furnace water can be carried out in various ways, including but not limited to: single chip microcomputer, general purpose

EXCEL calculation table, centralized sampling computer, manual or calculator calculation. According to this issue The basic principle of the definition, the calculation of the chloride ion content (C _C1 ) can also be carried out in various ways known in the art, such as manual or calculator calculation, calculation program compiled by general software (such as EXCEL), centralized computer. Calculation, calculation of single-chip microcomputer with sample-like function, calculation of conductivity table with sampling and calculation function of single-chip microcomputer, and so on.

A second aspect of the present invention provides a system for determining a corrosive acid radical anion content in a phosphate furnace water of a high-parameter steam drum furnace of a power plant, comprising a furnace water phosphate content determining unit and a furnace water hydrogen conductivity measuring unit, and The furnace water samples were separately introduced into the lines of the two measurement units.

In an embodiment of the assay system of the present invention, it may further comprise a calculation unit for performing data processing on the results of the furnace 7J the tablet acid content determining unit and the furnace water hydrogen conductivity measuring unit.

In an embodiment of the assay system of the present invention, wherein the calculating unit may be selected from the group consisting of: a centralized sampling computer or a single-chip microcomputer electrically connected to a furnace water phosphate content measuring unit and a furnace water hydrogen conductivity measuring unit, physically opposite Independent computer, integrated with the conductivity meter and electrically connected with the conductivity meter and the furnace water content determination unit, or integrated with the furnace water phosphate determination unit and with the conductivity meter and furnace The water phosphate content measuring unit is electrically connected to the single-chip microcomputer or the built-in single-chip microcomputer, and the built-in single-chip microcomputer which is integrated with the furnace water content determination unit and the conductivity meter and is electrically connected with the two.

In an embodiment of the assay system of the present invention, the furnace water hydrogen conductivity measuring unit may sequentially include a cation exchange column, an electrode cup, and a conductivity electrode in contact with the furnace water sample in the electrode cup along the flow direction of the furnace water sample. And a conductivity meter electrically connected to the conductivity electrode.

In one embodiment of the assay system of the present invention, wherein the furnace water phosphate content determining unit is an in-line phosphor meter. The online phosphorus meter is required to be configured by the relevant thermal power plant design code, and is therefore the most common measuring device for the furnace water phosphate; of course, the furnace water phosphate content determining unit can also adopt other forms or other methods. These methods include, but are not limited to, colorimetry, spectrophotometry, and the like.

In one embodiment of the assay system of the present invention, wherein the pressure, temperature and flow rate of the boiler water sample have been adjusted to the two determinations prior to entering the furnace water phosphate content determination unit and the furnace water hydrogen conductivity measurement unit The level at which the unit fits.

Various aspects of the assay and assay system of the present invention, and their benefits, are further described below.

All documents cited in the present invention include patent application specifications, patent specifications, references, technical standards, etc., the entire contents of which are hereby incorporated by reference, and if the The expression is subject to change. Moreover, the various terms and phrases used in the present invention have the ordinary meanings well known to those skilled in the art, and even though the present invention is intended to provide a more detailed description and explanation of the terms and phrases herein, such terms and phrases are Inconsistent with the well-known meaning, the meaning expressed in the present invention shall prevail.

The invention utilizes the principle of hydrogen conductivity and combines the results of phosphate determination to provide a new method and system for measuring the corrosive acid anion content of phosphate furnace water in a common content range (li^-lO g/L). Quantitative, semi-quantitative or on-line monitoring of corrosive acid radicals in phosphate furnace water to fill gaps in the prior art.

Specifically, the present invention first provides a method for determining the content of a corrosive acid bismuth anion used as an impurity in a phosphate furnace water for use in a phosphate furnace of a high-parameter (subcritical) steam drum furnace unit of a power plant. Monitoring of corrosive acid» anions in water. The principle of the method of the present invention is: determining the hydrogen ion conductivity (CC ^) of the furnace water at a standard temperature, and knowing the total contribution of all acids in the furnace water to the corresponding acid. At the same time, the phosphate content in the boiler water is measured, and then the phosphate hydrogen conductivity (CC _P04 ) corresponding to the phosphate content in the furnace water is subtracted from the hydrogen conductivity of the furnace water (CC), and the difference is all the corrosiveness in the furnace water. The acid anion corresponds to the acid contribution; the hydrogen ion conductivity difference is converted to obtain the corresponding corrosive acid anion content, and the hydrogenation difference can be directly used to characterize the corrosive acid anion content. This method can be used for manual analysis. , and can be used for online monitoring. Within the range of the common content of various corrosive acid anions in the furnace water, the phosphate corresponding phosphate only undergoes first-acid acid ionization, and the corresponding acid of other anions ionizes all hydrogen ions; the corresponding acid of these anions is as described above. The anions and cations produced by ionization can be considered to be in an infinitely diluted state, and they do not interact with each other. The contribution of each of them to the conductivity is consistent with the limit equivalent conductance, and their total contribution to the conductivity is additive.

The determination range of phosphate furnace water is 1-100 mg/L Cr using the National Standard of the People's Republic of China, GB 6905.3-86, Determination of Chloride in Boiler Water and Cooling Water Analysis Method. Using the "National Standard of the People's Republic of China, GB 6905.1-86, Determination of Chloride in Boiler Water and Cooling Water Analysis Method" The determination range of phosphate furnace water is 5-100 mg/L Cr. The determination range of the phosphate furnace water is 5-100 mg/L Cr using the National Standard of the People's Republic of China, GB 6905.2-86, Determination of Chloride of Boiler Water and Cooling Water Analysis Potentiometric Titration Method. The above three methods can not meet the needs of the chloride ion content in the phosphate furnace water of the high-parameter steam drum furnace of the power plant. Using the "National Standard of the People's Republic of China, GB/T 6905.4-93, Boiler Water and Cooling Water Analysis Method for Determination of Chloride by Coprecipitation and Preconcentration Spectrophotometry", the determination range of the brick furnace water is lO-lOOpg/L Cr However, this method is too complicated and has a narrow range. In summary, the above methods are not suitable for the daily monitoring and determination of the common content of chloride ions in the phosphate furnace water of the high-parameter steam drum furnace of the power plant, and even the continuous coverage of the measured concentration range cannot be formed. In addition, "National Standard of the People's Republic of China, GB/T 11446.7-1997, Determination of Chloride in Boiler Water and Cooling Water Analysis Ion Chromatography" can be used for Cr, S (V ² , P0 ₄ - in phosphate furnace water) ^{3 The} g/L measurement is performed, but the ion chromatography instrument is expensive, complicated, and requires high operation and maintenance, and is an off-line detection type instrument, which is not available in conventional power plants.

According to the description of the present invention, in particular, the examples provided by the embodiments of the present invention can be seen that the method of the present invention has the advantages of high speed, instant, and continuous online measurement; the method is sensitive, simple, reliable, economical, and effective in measuring a wide range of contents; The method of the invention can eliminate the effects of cations and phosphates, in the case of phosphate coexistence, common concentrations Corrosive acid anions in the range of (lO O^g/L) provide accurate, efficient determination and complete coverage. As can be seen from the above analysis, the assay method and assay system of the present invention have significant advantages over the prior art. DRAWINGS

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of one embodiment of a system for determining the corrosive acid anion content of a phosphate furnace water of the present invention.

Fig. 2 is a schematic view showing the measurement system of the first embodiment of the present invention.

Figure 3 is a schematic illustration of a measurement system of Example 2 of the present invention.

Figure 4 is a schematic illustration of a measurement system of Example 3 of the present invention.

Figure 5 is a schematic illustration of a measurement system of Example 4 of the present invention. detailed description

The invention is further illustrated by the following examples, which are to be construed as being in no way

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a specific embodiment of the system for determining the corrosive acid anion content of a phosphate furnace water according to the present invention, wherein a schematic diagram of the basic structure of the system is shown in detail. In this embodiment, an in-line phosphor table 3, a hydrogen conductivity meter 9 and a corresponding water sample line 2 are included, wherein the cation exchange column 5 is specifically increased in accordance with the present invention for use in phosphate furnace water. The hydrogen conductivity meter 9 as the furnace water hydrogen conductivity measuring unit includes a cation exchange column 5, an electrode cup 6, a conductivity electrode 7 and a conductivity meter 8, a cation exchange column 5, and a tube through which the electrode cup 6 passes the furnace water. The connection, the conductivity electrode 7 is in contact with the furnace water sample in the electrode cup 6, and the conductivity electrode 7 and the conductivity meter 8 are electrically connected. The on-line phosphorus meter 3, which is a furnace water content determination unit, is the most common method and apparatus for determining the phosphate content in the furnace water. In the present invention, the on-line phosphorus meter can be replaced by other phosphate analysis methods. The system of the invention can be conveniently used to determine a power plant A method for determining a corrosive acid radical anion content in a phosphate furnace water of a high-parameter steam drum furnace unit, the method comprising separately determining a phosphate content in a furnace water (C _P04 ) and a hydrogen conductivity after passing the furnace water through a cation exchange column (CC furnace water) And the step of determining the content of corrosive acid anion based on the measured phosphate content (C _P04 ) and hydrogen conductivity (CC furnace water).

As can be seen from Fig. 1, in combination with the measurement process, the furnace water sample 1 having adjusted the pressure, temperature and flow rate is respectively introduced into the furnace water hydrogen conductivity measuring unit and the furnace water phosphate content determining unit via the line 2; In the water-hydrogen conductivity measuring unit, the furnace water sequentially passes through the cation exchange column 5 and the electrode cup 6, and the conductivity meter 8 is electrically connected to the conductivity meter 8 and the conductivity electrode 7 in contact with the furnace water in the electrode cup 6. Determination of furnace water hydrogen conductivity CC furnace ^ measured furnace water wastewater 4 discharged to the wastewater ditch; in the furnace water phosphate content determination unit, the furnace water flows through the online phosphorus table 3 and determines the phosphate ion content C _P04 The measured boiler water wastewater 4 is discharged to the wastewater ditch. In the present embodiment, the cation exchange column 5, the electrode cup 6, the conductivity electrode 7, and the conductivity meter 8 can be integrated into a single hydrogen conductivity meter 9. The assay system according to the invention may further comprise a calculation unit for performing data processing on the measurement results of the two assay units; furthermore, the calculation unit may be arranged relatively independently or integrated with the conductivity meter and/or the on-line phosphor table Mode setting; the computing unit and its examples can be as detailed, for example, in the various computing elements provided in Figures 2 to 5 and the description of the following embodiments.

In the following examples, the system for determining the corrosive acid anion content of the phosphate furnace water is appropriately changed, and the furnace water in each case is separately measured by these deformation modes. Example 1: Determination of furnace water containing corrosive acid anions of the order of 10 ³ g/L using the method of the invention

In the present embodiment, the content of corrosive acid anions in the phosphate furnace water was measured using the measurement system shown in Fig. 2. It was determined that the chloride ion in the furnace water sample was the first acid anion with a content of 103⁄4 _g /L. The determination of hydrogen as a corrosive acid anion Conductivity cc acid group and corrosive acid anion represented by first acid anion mass concentration C $-acid radical _† Characterization of corrosive acid anion in gravel furnace water Contains the overall relationship of the measurement system shown in Figure 2 It is similar to the system shown in Figure 1. Among them, the data measured by the on-line phosphorus meter 3 and the conductivity meter 8 enter the centralized sampling computer 10, respectively. The cation exchange column 5 is installed at the inlet of the electrode cup 6 of the furnace water conductivity meter, and the hydrogen conductivity measurement data CC of the furnace water is collected by the computer 10 which is output by the centralized measurement of the conductivity meter 8. At the same time, the phosphate content in the furnace water is automatically determined by the on-line phosphorus meter 3, and the measured data C _P o ₄ is output from the on-line phosphorus meter 3, which is also collected by the sample computer. The centralized sampling computer 10 pre-programs the calculation program according to the basic principle, inputs and sets the relevant proportional coefficient, and calculates the CC water data and the C _P04 data collected at the same time to obtain the calculated value of C _CI .

The water sample of the furnace water is measured separately in two ways. After the first passage is passed through the cation exchange column 5, the hydrogen conductivity value CC water of the furnace water at the standard temperature is measured by the conductivity meter 8, and the CC furnace water data is output. The sampling computer 10 sets; the second way enters the online phosphorus table 3, the phosphate content C _P04 (calculated as Ρ0 ₄ ³ ·) in the furnace water is measured by the online phosphorus meter 3, and the C _P04 data is output, and the centralized sampling computer 10 Finally, the computer calculates the collected data according to the set formula and constant, and obtains the calculated value of the furnace water C _CI .

To verify the accuracy of the method of the present invention, the inventors performed ion chromatographic determination of the acid anion content of the 7 samples tested for comparison. Typical data is shown in Table 1.

Table 1 Determination of acid anion content in phosphate furnace water (measurement date: April 4, 2008)

C _C1 , the calculated value is calculated according to formula (1). In the calculation, the furnace water corrosive acid anion is counted as

Cl o

Cci, calculated = (CC furnace water - C _P04 , confirmed table · 0·00406) / 0·012 (1)

Calculate the hydrogen conductivity of corrosive acid anions according to formula (2) CC corrosive acid anions · CC corrosive acid anions - CC furnace water - CPO4, ^x0.00406 (2)

In formula (1) and formula (2): C _CI , calculated value and C _P04 , the unit of the table is pg / L; 0.00406 is the conversion coefficient of phosphate hydrogen conductivity, lpg / L PO - corresponds to 0.00406 S / cm; 0.012 It is the conversion coefficient of chloride ion hydrogen conductivity, lg/L Cr corresponds to 0.012 S/cm; CC humate anion and CC furnace water are all S/cm. Example 2: Determination of furnace water containing corrosive acid anions of the order of 5 x ¹² g/L using the method of the invention

In the present embodiment, the content of corrosive acid anions in the phosphate furnace water was measured using the measurement system shown in Fig. 3. It was determined that the chloride ion in the furnace water sample was the first acid anion with a content of 5xl0 _g /L; the determination was corrosive acid anion Hydrogen conductivity CC humic acid anion and corrosive acid anion represented by the first acid anion mass concentration C acid yt ^ characterize the content of corrosive acid anions in the furnace water.

The connection relationship of the assay system shown in Fig. 3 is generally similar to that of the system of Fig. 1, wherein the data measured by the on-line phosphor table 3 and the conductivity meter 8 can be manually input to the independent computer 11, respectively. In the inlet of the furnace water conductivity meter electrode cup 6, the cation exchange column 5 is installed, and the furnace water hydrogen conductivity data CC furnace water is automatically measured and output. At the same time, the online phosphorus meter automatically measures and outputs and displays the phosphate content C _{P04 in the} furnace water. According to the basic principle, a dedicated EXCEL calculation table containing a calculation program is pre-programmed in the computer 11, and CC and C _P04 data are manually input to the table, and the dedicated EXCEL calculation table automatically performs the calculation to obtain a calculated value of C _A .

The water sample of the furnace water is measured separately in two ways. After the first pass through the cation exchange column, the hydrogen conductivity value CC furnace _7j of the furnace water at the standard temperature is measured by the conductivity meter 8, and the measured value is displayed; Table 3, the phosphate content of the furnace water C _P04 (as PO ₄ ³ -) measured by the online phosphorus meter 3, and shows the measured value; the on-duty personnel record the meter according to the prescribed time, and manually calculate the CC boiler water and C _P04 data The dedicated EXCEL calculation table in the computer 11 is input, and the calculated value of the furnace water C _C1 is automatically calculated.

To verify the accuracy of the calculations of the present invention, the inventors performed ion chromatographic determination of the acid anion content of the water sample tested for comparison. Typical data is shown in Table 2.

Table 2 Determination of acid anion content in phosphate furnace water (measurement date: June 20, 2008)

Unit name: #1 unit The method of the invention

Ion chromatography

Sampling Cpo4, W CC Cci, CC relative error data /L

Time S/cm a difference %

C1 S0 ₄ ² PO4 ³

16:40 406 47 136 174 5.31 384 4.60 -5.51

18:00 423 41 158 153 5.78 430 5.16 1.63

Relative error, %=(C _C1 , Cci, *)/ Cci. *xl00% C _C1 , M is calculated according to formula (1). In the calculation, the furnace water corrosive acid anion is counted as

Cl o

Cci, calculated = (CC furnace water - C _P04 , phosphorus table x 0.00406) / 0.012 (1)

Calculate the hydrogen conductivity of corrosive acid anions according to formula (2) CC corrosive acid anions · CC corrosive acid anions = CC furnace water - Cpo4, table xO.00406 (2)

In formula (1) and formula (2): C _CI , calculated value and C _P04 , the unit of the table is μ ^ / L; 0.00406 is the conversion coefficient of phosphate hydrogen conductivity, ^ g / L P0 ₄ ³ - corresponds to 0.00406 pS /cm; 0.012 is the conversion coefficient of chloride ion hydrogen conductivity, lg / L Cl - corresponds to 0.012 S / cm; CC humate anion and CC furnace water are all S / cm. Example 3: Determination of furnace water containing corrosive acid anions of the order of 1 OVg/L using the method of the invention

In the present embodiment, the content of corrosive acid anions in the phosphate furnace water was measured using the measurement system shown in Fig. 4. It was determined that the chloride ion in the furnace water sample was the first acid anion anion, and the content was on the order of 10 g/L. The determination was based on the hydrogen conductivity of the corrosive acid anion, the CC acid anion and the first acid anion. Corrosive acid radical anion mass concentration C acid radical ^ Characterization of corrosive acid radical anion in phosphate furnace water The connection relationship of the assay system shown in Figure 4 is generally similar to the system shown in Figure 1; wherein the conductivity meter 8 and the built-in microcontroller 12 The integrated water gas corrosive acid analyzer 13 is installed; the data of the online phosphorus meter 3 is introduced into the built-in single chip microcomputer 12 for data processing. The system in this embodiment can be referred to as an integrated special furnace water corrosive acid» anion analyzer - the most basic part of which is a hydrogen conductivity meter: from the conductivity meter 8, the conductivity electrode 7 and the cation exchange column 5 and corresponding samples The water pipe 2 is composed for measuring CC ^, and the furnace water corrosive acid anion analyzer 13 also has the sampling and calculation functions of the single chip microcomputer 12. At the same time, there is an online map 3 automatically measured and output shows the phosphate content C _{P04 in the} furnace water. The furnace water corrosive acid anion analyzer 13 also collects the simultaneously engraved phosphorus while measuring the CC furnace water. Table 3 shows the phosphate content C _P04 in the furnace water, and the calculation and display output of C _C1 is completed by the preset calculation program of the single chip microcomputer 12.

To verify the accuracy of the calculations of the present invention, the inventors performed ion chromatographic determination of the acid anion content of the water sample tested for comparison. Typical data is shown in Table 3.

Table 3 Determination of acid anion content in phosphate furnace water (measurement date: February 28, 2008)

C _CI , calculation M is calculated according to formula (1). In the calculation, the furnace water corrosive acid anion is counted as

Cl o

Cci, calculated = (CC furnace water - C _P04 , 3⁄4x0.00406) / 0.012 (1)

Calculate the hydrogen conductivity of corrosive acid anions according to formula (2) CC Corrosive acid anions · CC Corrosive acid anions - CC furnace water - CPO4, 崎表 xO.00406 (2)

In formula (1) and formula (2): C _CI , calculated value and C _P04 , the unit of the table is g/L; 0.00406 is the conversion coefficient of phosphate hydrogen conductivity, lg/L P0 ₄ ^3- corresponds to 0.00406 S/cm 0.012 is the conversion coefficient of chloride ion hydrogen conductivity, lg / L Cr corresponds to 0.012 S / cm; CC rot acid anion and CC furnace water are all S / cm.

In this embodiment, the mass concentration ratio of the chloride ion and the sulfate ion is relatively small, so the instrument data is taken as an example to calculate the hydrogen conductivity percentage of the first acid anion, and the correction calculation is performed to illustrate the method and system of the present invention. The application when the specific gravity of the first acid anion is not dominant. (1) First, based on the ion chromatographic measurement result, the CC first acid anion % is calculated according to the formula (a).

CC first acid root P month ί5 sub %

= (G first acid anion ^x k first acid anion) / (G first acid anion ^x k first acid anion + C second acid anion ^x k second acid anion)

+ Ccixkc,)

= (34x0.012)/(14x0.00896+34x0.012)

= 77% < 80 %

(2) Calculate the corrected hydrogenation of the first acid anion by the formula (b) CC first acid anion, calibration.

= cc first acid anion % ^X (CC furnace water - GGpo4)

= 77 % x(1.72 - 330x0.00406)=0.29uS/cm

(3) Calculate the corrected mass concentration of the first acid anion according to formula (c) C. First acid anion, calibration o

C first acid anion, correction ⁼ CC first acid anion % ^X (CC furnace water - C! Gpo4) / k first acid anion (c)

= 77x(1.72 - 330x0.00406)/0.012 = 24ug/L

It should be noted that the correction calculation for this application example is merely illustrative and does not require a true correction of the calculation program. In the embodiment of the present invention, only in the case of an individual 10 ug/L level of corrosive acid ion content determination, the case where the CC first acid anion % < 80% occurs; within the range of 10'-lO'ug/L The vast majority of data, CC-acid radical _M % are in the normal range. Example 4: Determination of furnace water in an unstable state of corrosive acid anion concentration using the method of the present invention

In the present embodiment, the content of corrosive acid anions in the phosphate furnace water was measured using the measurement system shown in Fig. 5. It was determined that the chloride ion in the furnace water sample was the first acid anion, and the content was changed on the order of 10 ² -10 g/L. Characterization of corrosive acid anions in phosphate furnace water by the hydrogen conductivity CC acid anion of corrosive acid anion and the corrosive acid anion mass concentration C first acid anion represented by the first acid anion .

The connection relationship of the measurement system shown in FIG. 5 is generally similar to that of the system shown in FIG. 1; wherein the on-line phosphorus table 3, the conductivity meter 8 and the built-in single chip microcomputer 12 are integrated into a furnace salt. And the corrosive acid radical anion analyzer 14; the data of the on-line phosphorus meter 3 and the conductivity meter 8 are respectively introduced into the above-mentioned built-in single chip microcomputer 12 for data processing. The system in this embodiment can be referred to as an integrated special furnace water phosphate and corrosive acid anion comprehensive analyzer. The basic part is a hydrogen conductivity meter: from the conductivity meter 8, the conductivity electrode 7 and the cation exchange column 5 and corresponding samples. The water pipeline 2 is composed for measuring CC; at the same time, it also has an online phosphorus table 3 part automatic measurement and output showing the phosphate content C _{P04 in the} furnace water. The furnace water phosphate and corrosive acid-base anion analyzer 14 also has the sampling and calculation functions of the single-chip microcomputer, and automatically samples the CC and C _P04 data measured by the corresponding part, and calculates the C _C1 by the preset calculation program of the single-chip microcomputer. Display output.

To verify the accuracy of the calculations of the present invention, the inventors performed ion chromatographic determination of the acid anion content of the water sample tested for comparison. Typical data is shown in Table 4.

Table 4 Determination of acid anion content in phosphate furnace water (measurement date: March 28, 2008)

C _C1 . Calculated by equation (1). In the calculation, the furnace water corrosive acid anion is counted as

Cci, calculated = (CC furnace water - C _P04 , table Χ 0.00406) / 0·012 (1)

Calculate the hydrogen conductivity of corrosive acid anions according to formula (2) CC Corrosive acid anions ·

CC corrosive acid anion-CC furnace water - CPO4, ^x0.00406 (2)

In formula (1) and formula (2): C _a , calculated value and C _P04 , the unit of the table is g/L; 0.00406 is Phosphate hydrogen conductivity conversion factor, ^g/L P0 ₄ ^3- corresponds to 0.00406 S/cm; 0.012 is chloride ion hydrogen conductivity conversion factor, lpg/L Cl- corresponds to 0.012pS/cm; CC humate anion and CC 妒The unit of water is pS/cm. From the results in Tables 1-4 of Examples 1-4, it can be seen that:

1) The method of the present invention measures the corrosive acid ion content in the phosphate furnace water in the range of lO o g/L, and the relative error is less than 10%, which can be satisfied for the quantitative and semi-quantitative requirements required for actual monitoring.

2) Except for the rare water data of the order of 10 g/L, most of the water samples have a corrosive acid ion content of 10 ² -10 ³ g/L, and the chloride ion mass concentration is higher than that of sulfate. One order of magnitude higher, the effect of acid radicals is limited and no correction is required.

3) The method of the invention can effectively meet the requirement of determining the content of corrosive acid ion in the order of lO o^g/L in the phosphate furnace water, including the order of magnitude change of the corrosive acid ion content.

4) The method and system of the present invention determine the content of corrosive acid ions in the phosphate furnace water, the speed depends on the color development process of the phosphorus content on the phosphate content, generally 3-5 min; the determination process of the hydrogen conductivity of the furnace water is relatively shorter; Therefore, it can be quickly measured to meet the requirements of real-time and online monitoring. The above embodiments, although using different forms of assay systems of the present invention (e.g., different combinations of different computing units and computing units), are suitable for use in phosphate furnace waters.

10 ¹ to

Determination of the magnitude of corrosive acid anions.

Additionally, although in the above examples, the first acid anion in the phosphate furnace water is chloride ion, it will be apparent to those skilled in the art that the method and system of the present invention are equally applicable to the first acid anion in accordance with the principles of the present invention. The case of sulfate ions or other ions.

Claims

Rights request

1. A method for determining the content of corrosive acid anions in a phosphate furnace water of a high-parameter steam drum furnace of a power plant, the method comprising determining the phosphate content in the furnace water (C _P04 ) and the hydrogen conductance of the furnace water after passing through the cation exchange column The rate (CC furnace water) step, and the step of determining the content of corrosive acid anions based on the measured phosphate content (C _P04 ) and hydrogen conductivity (CC).

2. The method according to claim 1, which is suitable for effectively determining the content of corrosive acid anions in the order of lO O^g/L in a phosphate furnace water of a high-parameter unit of a power plant.

3. A method according to claim 1 wherein the phosphate content of the furnace water is determined by colorimetric, spectrophotometric, or in-line phosphorus spectrometry.

4. The method according to claim 1, wherein said corrosive acid anion is selected from one or more of a chloride ion, a sulfate ion, a carbonate ion, and an acetate ion.

5. A method according to any one of claims 1 to 4, wherein the content of said corrosive acid anion is characterized by the hydrogen conductivity of said corrosive acid anion (i.e., CC humate M), wherein said <:< : The acidity root is determined by the difference between the hydrogen conductivity of the furnace water (CC furnace water) and the hydrogen conductivity of the phosphate in the furnace water (CC _P04 ).

6. A method according to any one of claims 1 to 4, wherein the content of said corrosive acid anion is characterized by a mass concentration (C) of said corrosive acid anion; said method comprising determining the highest corrosivity in the furnace water a step of the acid anion as the first acid anion, and a step of determining the mass concentration (C) of the corrosive acid anion based on the first acid anion; the first acid anion is selected from the group consisting of chloride ion and sulfate ion Sub, carbonated, or acetate ions.

7. The method according to claim 6, wherein said method determines a phosphate furnace water of a high-parameter steam drum furnace of a power plant, and the applicable first acid anion content ranges from

Preferably, the first acid anion is a chloride ion.

The method according to any one of claims 1 to 4, wherein the content of the corrosive acid anion is characterized by a mass concentration of the first acid anion (i.e., a C-acid group), wherein the C-acid ion is The difference between the hydrogen conductivity of the furnace water (CC water) and the hydrogen conductivity of the phosphate in the furnace water (CC _P04 ) and the conversion factor of the first acid anion; the method is suitable for determining the amount of lO^lO^g L Grade 1 first acid anion power plant high-parameter steam drum furnace phosphate furnace water; Preferably, the first acid anion is chloride ion.

9. A system for determining a method for determining a corrosive acid anion content in a phosphate furnace water of a high-parameter steam drum furnace of a power plant according to claim 1, comprising a furnace water phosphate content determining unit and a furnace water hydrogen conductivity measurement a unit, and a conduit for separately introducing the furnace water sample into the two measurement units.

10. The system according to claim 9, wherein said furnace water hydrogen conductivity measuring unit comprises, in order of flow direction of the furnace water sample, a cation exchange column, an electrode cup, and a conductivity electrode in contact with the furnace water sample in the electrode cup. And a conductivity meter electrically connected to the conductivity electrode.

11. The system according to claim 9, wherein said furnace hydrous acid salt content determining unit is an in-line phosphor meter, a colorimeter or a spectrophotometer.

A system according to any one of claims 9 to 11, further comprising a calculation unit for performing data processing on the results of the furnace water phosphate content measuring unit and the furnace water hydrogen conductivity measuring unit.

13. The system according to claim 12, wherein said calculating unit is selected from the group consisting of: a single-chip microcomputer or a centralized sampling computer electrically connected to a furnace water content measuring unit and a furnace water hydrogen conductivity measuring unit, physically independent of each other The computer, the built-in single chip integrated with the conductivity meter and electrically connected with the conductivity meter and the furnace water phosphate content measuring unit, and the integrated setting with the furnace water phosphate content determining unit and the conductivity meter and the electrical properties of the two Connected to the built-in microcontroller.