Method of determination of concentration of sour products of organic impurities thermolysis in steam of direct-flow power boilers

FIELD: power engineering.

SUBSTANCE: invention is related to quantitative determination of content of potentially-sour organic impurities in feed water of direct-flow boilers and may be used in thermal power plants. Method includes measurement of specific electric conductivity values of cooled samples of live steam and feed water and estimation of concentration of solution components, at that measurement is carried out in samples that are passed through H-cationite filter, determination is carried out by difference of two measured values of specific electric conductivity of cooled samples, and design concentration of solution component is concentration of conventional acetic acid, determined form the ratio: Cac=153,6*χHLSHFW) where Cac - concentration of conventional acetic acid, mg/dm3; χHLS and -χHFW - specific electric conductivities of live steam and feed water, mCm/cm;.

EFFECT: increase of data information value, received from automatic conductivity meters.

2 tbl, 2 dwg

 

The invention relates to the quantitative determination of potentially acidic organic substances present in the feed water once-through boilers, which are in the process of vaporization are subjected to thermal decomposition with the formation of weak acids involved in corrosion processes on metals in contact with steam and its condensate, and can be used in thermal power plants.

Feed water once-through boilers with supercritical parameters is characterized by an almost complete absence of mineral impurities (conductivity χn<0,3 µs/cm) and the presence of small amounts of organic substances. In conditions of oxidative water-chemical mode when the oxygen concentration of 100 μg/kg 400 μg/kg and increasing the temperature from 300°With inlet and up to 550°at the exit of the boiler organic substances are subjected to deep thermal decomposition (thermolysis), often with the formation of acidic products of nature.

Organic matter comes in the feed water of boilers with the main condensate (oil products, degradation products can effectively block demineralization plant (BOU), the flowing cooling water in the condenser and circulating water in the network heaters) and with an extension in the ow of their reserve tank condensate. The most likely product of thermolysis of such substances is acetic acid. The emergence of acetic acid and other acidic substances character in a pair of once-through boilers increases the corrosivity of this environment and may cause corrosion damage to the tubes of the high pressure heaters (HPH) and line heaters using steam from a selection of durable part of the turbine.

Norms of quality of feed water and steam power boilers Russian TPP does not currently provide for the control of organic impurities - potentially acid substances, human papillomavirus (HPV) due to the lack of reliable measures.

Foreign plants such control is often conducted in terms of "Total organic carbon" (TOC) and Total inorganic carbon (TTC) in the feed water and steam, where the norm TOC 100 MCGS/kg [I. Martynov Behavior of organics and dissolved carbon dioxide in the steam path of the power plants. // Thermal engineering. 2002. No. 7. 67-70]. In the domestic power plants trying to estimate the number system for measuring conductivity and pH in the feed water and a couple of once-through boilers [Ways to improve water-chemical mode of the ACS units in the system OA "Sverdlovenergo" / Lavarella, Appalachia, Nailatikau etc. // Teploenergo the ka. 1999. No. 7. P.30-34]. This method is carried out measurements in a refrigerated samples automatic conductivity meters and pH meters with continuous flow of the sample through the sensor. For assessment of concentrations of PBA method uninformative due to mnogovektornosti influence on the electrical conductivity and pH from those in water and a pair of impurities, such as ammonia.

Analysis of changes χ and the pH in the feed water and a couple of once-through boilers of some power stations shows that the transition from the feed water to a couple of specific conductance of samples (or conductivity N-Nationalbank samples, if you are dosing of ammonia in the feed water) is increased from 0.05 µs/cm to 0.20 µs/cm and pH of the samples decreases by 0.1-0.3 units. Such changes are sustainable and are charged to thermolysis of organic impurities of the feed water [Michal A.S., Kevin J.S. gold, moor mud levels of Volatile Organic Acids and Carbon Diaxide in Steam / Water circnits. - Proc. Int. Con. Interaction of Organics and Organic Cycle Treatment Chemicals with Water, Steam. Germany, Stuttgart, 4-6 Oct. 2005].

There is a method of calculating the pH at power plants on the differential conductivity measurement before (direct conductivity samples, χ) and after H-cationite filter (the conductivity of H-acid samples, χn) [Analyzer FAM Deltacon pH. Technical data No. 23.14. Representation: ISPE. M]. Sushnost the method is in terms of differential conductivity (χ -χn) on the concentration of ammonia (ammonium hydroxide) and then to the concentration of hydroxyl ions, hydrogen ion concentration and the calculation pH=-lgCH+.

There is a method of determining the concentration of anions of weak acids - impurities in water (feed water, steam or condensate turbine) using liquid ion chromatography [On the application of chromatography for quality control of water and steam in thermal power plants. / Ohimaria, Weisensee, Auetralia etc. // thermal engineering. - 1996. No. 8. P.39-42], providing a quantitative determination of acetate, formate and other Cost of one industrial meter type IC Online is 150 thousand Euros.

There is a method of quality control feedwater largest conductivity direct water samples and samples of the previous N-cation column, this can be determined the total salinity of the feed water, the concentration of ammonia and carbon dioxide [RF Patent №2168172. The method of controlling the quality of the condensate and feedwater. // Naeemia, Vgie, Antonadou and other M: of the Invention. 2001. No. 13].

The disadvantages of these methods are the lack of a definition of organic matter by measuring the conductivity and the use of expensive and complex equipment (automatic ion chromatograph).

Known taken as a prototype method of control for the I content of corrosive and hazardous organic compounds in the water steam circuit of the power unit with a steam boiler at a ratio χ OPPWthe conductivity values, respectively, steam and feed water, compared with a given limit of such relationships separately for evaporating and superheating sections sections of the boiler. The excess ratio χOPPWat the evaporative sites above 1,3 and superheating above 1.15 indicates the presence of products of thermolysis of organic substances of an acidic nature [RF Patent №2231778. The method of control over the content of corrosive and hazardous organic compounds in water steam path of a thermal power plant. // Weinmann A.B., Malakhov I.A. Published 2004.06.27].

The disadvantage of this method is the necessity of measuring the conductivity of the cooled fluid samples after each temperature zone of the boiler: up to 160°; 280°S; up to 440°S; up to 545°and the result only of qualitative nature without quantitative determination of the concentration of organic substances or products of their thermal conversion.

The technical result of the invention is to increase the information content of data from automated instruments conductometric control through the quantification of the content of the acidic products of thermolysis of organic impurities in a pair straight-through energy is ski boilers in terms of the concentration of acetic acid. The technical result is achieved by the fact that they measure conductivity of H-acid samples of feed water and steam flow power boiler and the resulting data is used to calculate the concentration of the acidic products of thermolysis of organic impurities of the feed water in terms of the concentration of acetic acid.

The electroneutrality equation is written in the following form:

a) for H-acid samples sharp pair

b) for H-acid samples feed water

In equations (1) and (2) the concentration of sodium ions and chloride in the feed water and the pair are equal, i.eandfrom the condition of full transition of these impurities from the water into steam. Then the difference equations (1) and (2) gives the expression

The concentration of the acetate ion [CH3Soo-] in equation (3) can be taken approximately equal to the total concentration of acetic acid, ie [SN3Soo-]=CMC. For H-acid cooled sample pair at normal pH values of about 6.0 and above, the ratio of [SN3Soo-]/[CH3COOH] is 20:1 or more, and therefore adopted the assumption is true, within 5% error.

Urav the value of electrical conductivity in the N of the acid sample is written in the following form:

a) for sharp pair

b) for feedwater

With account taken of the above assumptions, the difference equations (4) and (5) by substituting the expression (3) allows to obtain the expression (6):

whereand- measured the conductivity of H-acid samples direct steam and feedwater µs/cm;tabular values of the limiting electric mobility of ions H+HCO3-CH3Soo-.

The concentration of acetic acid in chilled N acid sample pair is usually significantly larger than the change in concentration of hydrocarbons with transition from feed water to steam, ie:

Then the second summand in the right part of equation (6) can be neglected and resolve it relative to the concentration of acetic acid in the form of equation (8), µmol/DM3:

which for 25°acquires a simple form, µmol/DM3:

where,- reduced to 25°With the conductivity of N-Nationalbank samples sharp is th steam and feed water.

In this case, equation (9) gives the concentration of potentially acidic substances in the feed water ow through the boiler, expressed through the concentration of acetic acid in a pair of the boiler on the measured values of conductivity N-Nationalbank chilled samples of steam and feed water. If no ammonia is dosed into the feed water, the calculation according to equation (9) can be made for values of conductivity as N-Nationalbank and direct sampling direct steam (and feedwater

Typically, the concentration of impurities in the feed water of boilers expressed in µg/DM3. Then from equation (9) we can obtain the following expression for the concentration conditional acetic acid, mg/DM3:

To test the indirect holding instrument is used to measure the complex for modeling samples of feed water and steam flow boiler (figure 1). The instrument consists of two ionoobmennyh filters: H-cationite (1) and HE is anionite (2) for deep demineralization of distilled water, metering device (3) and the measuring unit containing sensors of conductivity meters to N-columns (4) and after (χ and χN).

Distilled water is supplied to the H-cationite Phil is Tr (1) and HE is anionite filter (2) for doonesbury. Demineralized water after H-HE-ionite filters has high quality (χ=0,2 to 0.15 µs/cm) and very low concentration of mineral salts. After dosing solution (3) (ammonia and acetic acid to simulate a sample pair) measured specific conductance (χ) mixed solution (direct test), and then water is supplied to the N-column (HR1). After N-columns measured conductivity N-the acid test (χN), and the water enters the tank demineralized water.

When mixing is simulated aqueous fluid containing ammonia and formed during thermolysis of organic impurities acetic acid. The solution is neutralized one of these components being less equivalent concentration. However, in the solution are cations NH4+and anions SN3COO-. When you pass such an extremely dilute solution through a column of N-cation cations NH4+replaced by cations of H+from the cation exchanger, which again returns the acetate ions in equilibrium with acetic acid.

Preparation of solution of a mixture of ammonia and acetic acid for dosing in globalisasyon water produced by the introduction of a solution of acetic acid in a solution of ammonia. However, this is not significant in view of the subsequent pass is extremely dilute solution of a mixture through a cation exchange resin in H-form ion replacement NH 4+ions H+and neutralization of OH--ions.

The results of the experiments are presented in table format (table 1) and graphical dependency conductivity of H-acid samples (figure 2) on the concentration of acetic acid at various concentrations of ammonia in the samples. Whence it is seen that the conductivity of H-acid samples yields a stable linear dependenceand little depends on the concentration of ammonia in the sample (this cannot be said about a similar line of direct sample - see table 1, columns 3 and 5).

Calculated values WithMCon average within 15% of the variance are consistent with the measured values of acetic acid (table 1).

The proposed method was used for calculation of the concentration of potentially acidic substances in the feed water reactors with once-through boilers Konakovo and Permskaya GRES. Some results are given in table 2 and are consistent with data from studies found in the literature.

Thus, the proposed method of determining the concentration of the acidic products of thermolysis of organic impurities in a pair of once-through boilers at CHP can increase the information content of data from automated instruments, and to quantify the content of these substances in terms of the concentration at ssnoi acid.

Table 1
Some results of measurements of electrical conductivity and calculate the concentration of acetic acid on laboratory tests of water samples
Reading devicesThe measured concentrationThe estimated concentrationΔCMC, %
Source waterAfter dosing
χχNχχNµg/DM3WithMCµg/DM3WithMCµg/DM3
0,270,250,220,48-2534,7+38,8
0,280,270,210,45-2427,9+16,4
0,190,150,280,57-6063,9+6,48
0,150,240,460,85-9093,2+to 3.58
0,120,220,250,3619,27,78,3+7,66
0,130,230,270,4119,22327,3+18,8
0,150,240,320,6519,27862,5-19,9
0,150,320,530,524527,229,9+10,1
0,140,310,420,934510896,1or 11.3
Average error:14,78
Note. Units χ and χN- µs/cm; CMC=

Table 2
The results of the calculation of the concentration of acetic acid program authors for units with once-through boilers
Measured valueThe estimated value
pHPWχN, RO,

µs/cm
χPW,

µs/cm
pHOPχN, OP,< / br>
µs/cm
,

ág/l
,

ág/l
8,1790,0900,407,970,1321,16,14
8,0830,0830,287,740,1410,38,76
8,080,1000,317,870,1613,8which 9.22
8,300,1030,5938,010,12538,03,38
7,990,0800,287,90,1114,9to 4.62
6,600,1880,1536,50,23006,40
6,600,2140,1766,50,27208,90

The method of determining the concentration of the acidic products of thermolysis of organic impurities in a pair of once-through boilers, including the measurement values of the conductivity of the cooled samples sharp pair is nutritional and the th water and calculating the concentration of the components of the solution, characterized in that the measurement is performed in samples passed through the H-cationite filter, the determination is done according to the difference of the two measured values of the conductivity of the cooled samples, and the estimated component concentration of a solution is the concentration of conventional acetic acid determined from the relationship

WithMC=153,6·(χnOP-χnPW),

where CMC- concentration conditional acetic acid, mg/DM3;

χnOPand χnPW- conductivity steam and feedwater µs/see



 

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