CN114910519A - Method and system for detecting conductivity of degassed hydrogen - Google Patents
Method and system for detecting conductivity of degassed hydrogen Download PDFInfo
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Abstract
The invention belongs to the technical field of water quality detection, and particularly relates to a degassed hydrogen conductivity detection method and a degassed hydrogen conductivity detection system.
Description
Technical Field
The invention belongs to the technical field of water quality detection, and particularly relates to a method and a system for detecting the conductivity of degassed hydrogen.
Background
The hydrogen conductivity is the most key monitoring index of a water vapor system of a generating set or steam power equipment and is mainly used for reflecting the total amount of corrosive anions in a water vapor sample. If the water sample contains CO 2 The carbonate formed after the water sample passes through the cation exchange column has conductivity, and particularly for gas and air cooling units, the situation that the hydrogen conductivity exceeds the standard but the anion content is qualified generally exists. Thus for this type of situation, the hydrogen conductivity of the water sample degassing (water sample CO removal) is measured 2 The later hydrogen conductivity) can more accurately reflect the total amount of corrosive anions, so that the standards such as DL/1717-.
At present, instruments for measuring the electrical conductivity of degassed hydrogen adopt certain technical means to carry out degassing treatment on a water sample passing through a cation exchange column. The technical means is generally a heating boiling method or a vacuum film method. The heating boiling method needs to heat a water sample to boiling and then cool the water sample, the measuring system is complex, the energy consumption is high, the failure rate of the heating module is high, and the cooled water temperature is about 50 ℃, which is not beneficial to the accurate measurement of the conductivity; the degassing efficiency of the vacuum membrane method is influenced by comprehensive factors such as the flow rate of a water sample, the running state of the membrane, the vacuum degree and the like, and the degassing efficiency is poor in stability.
Disclosure of Invention
The invention aims to provide a method and a system for detecting the conductivity of degassed hydrogen, which can obtain the conductivity of the degassed hydrogen of a raw water sample by calculating after only measuring the hydrogen conductivity of the raw water sample and the hydrogen conductivity of a dilution water sample.
The technical problem solution of the invention is as follows:
a method for detecting the conductivity of degassed hydrogen is characterized by comprising the following steps:
1) removing cations in the raw water sample;
1) removing cations in the raw water sample;
2) measuring the water sample obtained in the step 1) and removing anions in the water sample;
3) measuring the water sample in the step 1) and measuring the conductivity index CC of the water sample 1 ；
4) Measuring the conductivity index CC of the mixed water sample after mixing the water sample obtained in the step 2) with the water sample in the step 3) 2 ；
5) And calculating the degassed hydrogen conductivity DCC of the water sample in the original water sample.
Further defined, the step 4) comprises the following steps:
4.1) comparing the volume ratio of the water sample obtained from the step 2) and the water sample obtained from the step 3) according to the ratio of 1: (n-1), wherein n is more than or equal to 2;
4.2) measuring the conductivity index CC of the mixed water sample obtained in the step 4.1) 2 。
Further limiting, in the step 4.1), n is more than or equal to 2 and less than or equal to 5.
Further limiting, the step 5) is specifically:
firstly, the contribution value of corrosive anions in the original water sample to the hydrogen conductivity is set as A 1 ，CO 2 The contribution to the hydrogen conductivity is B 1 (ii) a The contribution of anions in the mixed water sample to the hydrogen conductivity is A 2 ，CO 2 The contribution to the hydrogen conductivity is B 2 CO in the crude water sample 2 The concentration is C;
secondly, according to
To obtain CO 2 The contribution to hydrogen conductivity can be expressed as a function of concentration as
Binding n.CC 2 -CC 1 (n-1) × 0.0545+ nf (C/n) -f (C) to give the value of C;
finally, according to f (C) ═ -10 -17 C 6 +4×10 -14 C 5 -5×10 -11 C 4 +3×10 -8 C 3 -10 -5 C 2 +0.0036C +0.0022 to obtain a degassed hydrogen conductivity value DCC ═ CC of the raw water sample 1 -B 1 ＝CC 1 -f(C)。
The degassed hydrogen conductivity detection system is characterized by comprising an electric automatic cation exchange device connected with an output end of a raw water sample, a first conductivity detector and an electric automatic regeneration anion exchange device which are simultaneously connected with an output end of the electric automatic cation exchange device, and a second conductivity detector which is simultaneously connected with an output end of the first conductivity detector and an output end of the electric automatic regeneration anion exchange device.
Further defined, the ratio of the flow rate of the sample water between the automatic cation exchange device and the first conductivity detector to the flow rate of the sample water between the automatic cation exchange device and the automatic regeneration anion exchange device is 1: (n-1), wherein n is more than or equal to 2.
Further limited, n is more than or equal to 2 and less than or equal to 5.
The invention has the beneficial effects that:
the degassed hydrogen conductivity of the original water sample can be obtained through calculation only by measuring the hydrogen conductivity index of the original water sample after the cation water sample is removed and the hydrogen conductivity index of the diluted cation water sample is removed, the method is simple, the measurement efficiency is improved, the measurement difficulty is prevented from being increased by using a vacuum membrane method or a heating boiling method, the factor influencing the conductivity measurement accuracy is also prevented from being added, and the measurement result is accurate.
Drawings
FIG. 1 is a schematic structural diagram of a system according to embodiment 2 of the present invention;
in the figure, 1, an automatic cation exchange device; 2. a first conductance detector; 3. an electrically automatic regenerating anion exchange device; 4. a second conductance detector.
Detailed Description
Example 1
A degassed hydrogen conductivity detection method comprises the following steps:
1) removing cations in the original water sample;
specifically, the cation in the original water sample is firstly removed, the cation exchange column can be selected in the method for removing the cations in the original water sample, the cations can also be removed through an electric automatic regeneration cation exchange device, the electric automatic regeneration cation exchange device is preferably used for removing the cations, frequent replacement is avoided, and the water sample with the removed cations is obtained after the completion of the removal of the cations, and can be called as a cation-removed water sample.
2) Measuring the water sample obtained in the step 1) and removing anions in the water sample;
specifically, after the cation-removed water sample obtained in step 1) is taken, all anions in the cation-removed water sample are removed, the method for removing anions can also be implemented by using an anion exchange column or using an electrically automatic regeneration anion exchange device, preferably the latter, after the cations and the anions are removed from the original water sample, the content of impurities in the original water sample is considered to be extremely low, and the water sample obtained at this time can be considered to be pure water.
3) Measuring the water sample in the step 1 and measuring the conductivity index CC of the water sample 1 ；
Specifically, the cation-removed water sample obtained in the step 1) is taken, then the hydrogen conductivity index of the cation-removed water sample is measured, the measurement can be carried out by the existing conductivity detector, and the hydrogen conductivity index of the cation-removed water sample obtained by the measurement is CC 1 。
4) Mixing the water sample obtained in the step 2) with the water sample obtained in the step 3) to measure the conductivity index CC of the water sample 2 ；
The step 4) comprises the following steps:
4.1) comparing the volume ratio of the water sample obtained from step 2) to the water sample obtained from step 3) according to a ratio of 1: (n-1), wherein n is more than or equal to 2;
specifically, the pure water obtained from the step 2) and the decationized water for measuring the hydrogen conductivity index obtained from the step 3) are mixed according to the ratio of 1: (n-1) in the case where the sample is diluted n times, where n.gtoreq.2, preferably 2. gtoreq.n.gtoreq.5.
4.2) measuring the conductivity index CC of the mixed water sample obtained in the step 4.1) 2 ；
Specifically, after the mixed water sample of the step 4.1) is obtained, the hydrogen conductivity index of the mixed water sample is measured again, and the measurement result is CC 2 And discharging the mixed water sample after the measurement is finished.
5) Calculating the degassed hydrogen conductivity DCC of the water sample in the original water sample;
specifically, first, the contribution value of corrosive anions in the original water sample to the hydrogen conductivity is set as A 1 ，CO 2 The contribution to the hydrogen conductivity is B 1 The contribution of anions in the mixed water sample to the hydrogen conductivity is A 2 ，CO 2 The contribution to the hydrogen conductivity is B 2 CO in raw water sample 2 The concentration is C;
secondly, according to
CO can be obtained 2 The contribution to hydrogen conductivity can be expressed as a function of concentration as
Binding n.CC 2 -CC 1 (n-1) × 0.0545+ nf (C/n) -f (C) to give the value of C;
finally, according to f (C) ═ -10 -17 C 6 +4×10 -14 C 5 -5×10 -11 C 4 +3×10 -8 C 3 -10 -5 C 2 +0.0036C +0.0022, the degassed hydrogen conductivity value DCC of the raw water sample was obtained as CC 1 -B 1 ＝CC 1 -f(C)。
The following 2 sets of tests were performed:
in experiment 1, a water sample is divided into 2 groups with equal volumes, wherein the first group of water samples are measured by the conventional method to obtain the degassed hydrogen conductivity DCC of the water sample Measuring Directly measuring the hydrogen conductivity index CC of the water sample of the second group of water samples as 0.357 mu S/cm 1 The value is 0.909μS/cm；
Then, when taking n as 3, adding pure water with the capacity 2 times that of the water sample into the second group of water samples, so that CO in the water samples is obtained 2 The concentration is diluted by 3 times, and then the hydrogen conductivity CC of the mixed water sample is measured 2 0.419. mu.S/cm, n.CC passage 2 -CC 1 (n-1) × 0.0545+ nf (C/n) -f (C) gave a C value of 300 μ g/L, followed by f (C) -10 ═ C -17 C 6 +4×10 - 14 C 5 -5×10 -11 C 4 +3×10 -8 C 3 -10 -5 C 2 +0.0036C +0.0022 to obtain CO 2 The contribution value of the hydrogen conductivity of the second group of water samples before dilution is B 1 0.555. mu.S/cm, finally, according to DCC CC 1 -B 1 ＝CC 1 F (C) obtaining the degassed hydrogen conductivity value DCC of the original water sample Computing And (3) the concentration is 0.354 mu S/cm, and the measurement requirement is met.
Similarly, in experiment 2, n is 4, and the steps are adopted to measure the degassed hydrogen conductivity DCC of the water sample Measuring 0.259 mu S/cm, hydrogen conductivity CC of water sample 1 Hydrogen conductivity CC of water sample diluted 4 times as high as 0.910 mu S/cm 2 The concentration of carbon dioxide in the water sample was calculated to be about 400. mu.g/L at 0.370. mu.S/cm, and the contribution B to the hydrogen conductivity was obtained 1 DCC is obtained by final calculation at 0.655 muS/cm Computing The concentration is 0.255 mu S/cm, and the measurement requirement is met; the results of the two sets of tests are shown in table 1:
table 1 raw water sample degassing hydrogen conductivity detection calculation table
It can be found that the calculation result substantially coincides with the actual measurement result.
Example 2
Referring to fig. 1, a degassed hydrogen conductivity detection system includes an automatic cation exchange device 1 connected to an output end of a raw water sample, a first conductivity detector 2 and an automatic anion exchange device 3 connected to an output end of the automatic cation exchange device 1, and a second conductivity detector 4 connected to an output end of the first conductivity detector 2 and an output end of the automatic anion exchange device 3, where a ratio of a flow rate of sample water between the automatic cation exchange device 1 and the first conductivity detector 2 to a flow rate of sample water between the automatic cation exchange device 1 and the automatic anion exchange device 3 is 1: (n-1), wherein n is more than or equal to 2 and less than or equal to 5.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, and the terms used herein in the specification of the present invention are for the purpose of describing particular embodiments only and are not intended to limit the present invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Claims (7)
1. A method for detecting the conductivity of degassed hydrogen is characterized by comprising the following steps:
1) removing cations in the raw water sample;
2) measuring the water sample obtained in the step 1) and removing anions in the water sample;
3) measuring the water sample in the step 1) and measuring the conductivity index CC of the water sample 1 ；
4) Measuring the conductivity index CC of the mixed water sample after mixing the water sample obtained in the step 2) with the water sample in the step 3) 2 ；
5) And calculating the degassed hydrogen conductivity DCC of the water sample in the original water sample.
2. The degassed hydrogen conductivity detection method according to claim 1, wherein the step 4) comprises the steps of:
4.1) mixing the water sample obtained from the step 2) and the water sample obtained from the step 3) according to the volume ratio of 1: (n-1), wherein n is more than or equal to 2;
4.2)measuring the conductivity index CC of the mixed water sample obtained in the step 4.1) 2 。
3. The method for detecting the conductivity of degassed hydrogen according to claim 2, wherein in step 4.1), n is 2. ltoreq. n.ltoreq.5.
4. The method for detecting the conductivity of degassed hydrogen according to claim 2, wherein the step 5) is specifically performed by:
firstly, the contribution value of corrosive anions in the original water sample to the hydrogen conductivity is set as A 1 CO in raw water sample 2 The concentration is C, and CO is in the raw water sample 2 The contribution to the hydrogen conductivity is B 1 (ii) a The contribution of anions in the mixed water sample to the hydrogen conductivity is A 2 CO in mixed water sample 2 The contribution to the hydrogen conductivity is B 2 ；
Secondly, according to
To obtain CO 2 The contribution to hydrogen conductivity can be expressed as a function of concentration as
Binding n.CC 2 -CC 1 (n-1) × 0.0545+ nf (C/n) -f (C) to give the value of C;
finally, according to f (C) ═ -10 -17 C 6 +4×10 -14 C 5 -5×10 -11 C 4 +3×10 -8 C 3 -10 -5 C 2 +0.0036C +0.0022 to obtain a degassed hydrogen conductivity value DCC ═ CC of the raw water sample 1 -B 1 ＝CC 1 -f(C)。
5. The degassed hydrogen conductivity detection system is characterized by comprising an automatic electric cation exchange device (1) connected with an output end of a raw water sample, a first conductivity detector (2) and an automatic electric regeneration anion exchange device (3) which are respectively connected with an output end of the automatic electric cation exchange device (1), and a second conductivity detector (4) which is simultaneously connected with an output end of the first conductivity detector (2) and an output end of the automatic electric regeneration anion exchange device (3).
6. The degassed hydrogen conductivity detection system according to claim 5, wherein the ratio of the flow rate of sample water between the automatic cation exchange device (1) and the first conductivity detector (2) to the flow rate of sample water between the automatic cation exchange device (1) and the automatic regenerable anion exchange device (3) is 1: (n-1), wherein n is more than or equal to 2.
7. The degassed hydrogen conductivity detection system of claim 6, wherein n is 2 ≦ n ≦ 5.
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| CN115902004A (en) * | 2022-11-08 | 2023-04-04 | 中科特肯(山东)智能科技有限公司 | Measuring device and measuring method for conductivity of degassed hydrogen |
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| CN115902004A (en) * | 2022-11-08 | 2023-04-04 | 中科特肯(山东)智能科技有限公司 | Measuring device and measuring method for conductivity of degassed hydrogen |
| CN115902004B (en) * | 2022-11-08 | 2023-08-18 | 中科特肯(山东)智能科技有限公司 | Measurement device and measurement method for conductivity of degassed hydrogen |
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