CN114910518A - Method and system for detecting content of dissolved carbon dioxide in water vapor - Google Patents
Method and system for detecting content of dissolved carbon dioxide in water vapor Download PDFInfo
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Abstract
The invention belongs to the field of water quality detection, and relates to a method for detecting the content of dissolved carbon dioxide in water vapor, which comprises the following steps: 1) preparing n standard samples; 2) sequentially measuring conductivity values corresponding to the n standard samples; 3) taking the mass concentration of the carbon dioxide as a vertical axis and the corresponding conductivity value as a horizontal axis to obtain a standard curve equation; 4) performing ion exchange and degassing treatment on a water sample to be detected to obtain pure water containing carbon dioxide, detecting the conductivity value, and substituting the conductivity value into a standard curve equation to obtain the content of the carbon dioxide in the water sample to be detected; meanwhile, a detection system is also provided, the automation degree is high, and the operation is simple and convenient. The method can realize the automatic detection of the content of the carbon dioxide, has short detection time and low detection limit, ensures the accuracy of the hydrogen conductivity of a water vapor system, and is safe and environment-friendly.
Description
Technical Field
The invention belongs to the field of water quality detection, and relates to a method and a system for detecting the content of dissolved carbon dioxide in water vapor.
Background
The hydrogen conductivity monitoring index is an important supervision index of a power station water vapor system. The hydrogen conductivity is an index for indirectly reflecting anions in water by removing cations in water through a cation resin exchange column, and the index can be influenced by carbon dioxide dissolved in water vapor and cannot truly reflect the true condition of the anion index, so that the detection of the content of trace carbon dioxide has important significance for distinguishing the true level of harmful anions.
At present, two methods for measuring carbon dioxide in power station water quality monitoring are mainly adopted: direct method (DL502.7-2006) and immobilization method (DL 502.8-2006). The direct method is that a burette with an alkaline asbestos absorption device is utilized to directly measure carbon dioxide dissolved in water by using a sodium hydroxide standard solution, and when the carbon dioxide and the sodium hydroxide completely generate sodium bicarbonate, the pH value of the solution is about 8.3, so phenolphthalein is used as an indicator, and the condition that the sodium hydroxide standard solution is dripped to reddish color is an end point, but the method is not suitable for water samples containing other acidic substances except the carbon dioxide; the fixing method is that a water sample directly flows into a sampling bottle which is added with a certain volume of sodium hydroxide standard solution in advance, free carbon dioxide in water is converted into carbonate by the sodium hydroxide to be fixed, then the carbonate is neutralized and back titrated by sulfuric acid standard solution, and the content of the free carbon dioxide in the water is calculated, but the method is suitable for measuring the outlet water of the hydrogen ion exchanger and the inlet water of the carbon remover, and the measuring error is +/-0.5 mg/L.
Therefore, the two existing detection methods have complex detection process, each sampling is used for detection, and the detection time is long; the detection limit is high, the method is suitable for testing the content of mg/L-level carbon dioxide, the content of dissolved carbon dioxide in the water vapor circulation of a power station is very small, generally in the mu g/L level, the error is large by adopting the existing method, and the detection cannot be carried out, but the accuracy of the hydrogen conductivity is influenced by the circulation of trace carbon dioxide in the water vapor.
Disclosure of Invention
Aiming at the technical problems existing in the detection of the content of dissolved carbon dioxide in water vapor, the invention provides the method and the system for detecting the content of dissolved carbon dioxide in water vapor, which can realize the automatic detection of the content of carbon dioxide, have short detection time and low detection limit, ensure the accuracy of the hydrogen conductivity of a water vapor system, and are safe and environment-friendly.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for detecting the content of dissolved carbon dioxide in water vapor comprises the following steps:
1) preparing n standard samples with carbon dioxide mass concentrations of C1, C2 and … … Cn respectively;
2) sequentially measuring the conductivity values sigma 1, sigma 2 and … … sigma n corresponding to the n standard samples in the step 1);
3) taking the mass concentration C1, C2 and … … Cn of the carbon dioxide as the vertical axis and the corresponding conductivity values sigma 1, sigma 2 and … … sigma n as the horizontal axis of the n groups of data obtained in the step 2), drawing a standard curve of the mass concentration and the conductivity of the carbon dioxide, and obtaining a standard curve equation of C559.8 sigma 3 +308.8σ 2 +162.2σ-5.07；
4) And (3) carrying out ion exchange and degassing treatment on the water sample to be detected containing the carbon dioxide to obtain pure water containing the carbon dioxide, detecting the conductivity value sigma ' of the pure water containing the carbon dioxide, and substituting the sigma ' into the standard curve equation in the step 3) to obtain the mass concentration C ' of the carbon dioxide in the water sample to be detected.
Further, the specific processes of the ion exchange and degassing treatment in the step 4) are as follows:
4.1) carrying out cation exchange on the water sample to be detected to obtain the water sample to be detected containing anions;
4.2) dividing the water sample to be detected containing anions into two paths, wherein one path of water sample is subjected to anion exchange to obtain pure water and then passes through a degassing membrane; the other path directly passes through a degassing membrane;
4.3) passing the pure water and the water sample to be detected containing anions through a degassing membrane to obtain the pure water containing carbon dioxide.
Further, in the step 4.3), the pure water and the water sample to be tested containing anions correspondingly pass through the two sides of the degassing membrane, respectively, and carbon dioxide in the water sample to be tested containing anions enters the pure water through the degassing membrane to obtain the pure water containing carbon dioxide.
A detection system for realizing the method for detecting the content of dissolved carbon dioxide in water vapor comprises a cation exchanger, an anion exchanger, a carbon dioxide degassing device and a second conductivity meter which are sequentially communicated; the cation exchanger is also in communication with a carbon dioxide degasser.
Further, the carbon dioxide degassing device comprises a shell and a degassing membrane arranged on the cross section of the shell; the degassing membrane divides the housing into a first chamber and a second chamber; the first chamber is in communication with a cation exchanger; the second chamber is respectively communicated with the anion exchanger and the second conductivity meter.
Further, the cation exchanger is an electrically regenerated cation exchanger.
Further, the anion exchanger is an electrically regenerated anion exchanger.
Further, the degassing membrane is a carbon dioxide degassing membrane.
Further, the detection system further comprises a first conductivity meter disposed between the anion exchanger and the second chamber.
Further, the detection system also comprises a power supply which is respectively connected with the cation exchanger, the anion exchanger, the first conductivity meter and the second conductivity meter.
The invention has the beneficial effects that:
1. according to the method for detecting the content of the carbon dioxide dissolved in the water vapor, firstly, a curve equation of the mass concentration and the conductivity of the carbon dioxide is made, then, a water sample to be detected is processed by utilizing the electrodialysis and ion migration principles to obtain pure water, dissolved carbon dioxide in water is dissolved into the pure water by utilizing a carbon dioxide degassing membrane, the conductivity of the pure water containing the carbon dioxide is measured, and the carbon dioxide content in the water sample to be detected is obtained by substituting the measured conductivity into the curve equation.
2. The detection method provided by the invention can detect the trace carbon dioxide content in the water sample, the detection limit is mu g/L, the detection limit is low, and the detection requirement of carbon dioxide in the water vapor circulation of the power station can be met.
3. According to the detection method, the content of the carbon dioxide is directly calculated through instrument detection and a curve equation, a chemical reagent is not needed, the contact of workers with dangerous chemicals is avoided, the detection method is environment-friendly, the measurement error is small, and the result is accurate.
4. The detection device provided by the invention comprises a cation exchanger, an anion exchanger, a degassing membrane and a conductivity meter, wherein the cation exchanger is an electrically regenerated cation exchanger; the anion exchanger is an electrically regenerated anion exchanger, the detection system is simple, automatic detection can be realized, the detection time is short, data support can be timely provided for steam medium circulation of a power station, and the accuracy of the hydrogen conductivity is ensured.
Drawings
FIG. 1 is a schematic structural diagram of a detection apparatus according to the present invention;
FIG. 2 is a schematic diagram of a carbon dioxide degasser according to the present invention;
FIG. 3 is a graph of a standard curve between conductivity σ and carbon dioxide concentration according to the present invention;
wherein:
1-a cation exchanger; 2-an anion exchanger; 3-a first conductivity meter; 4-carbon dioxide degasser; 41-a housing; 42-degassing the membrane; 43 — a first chamber; 44 — a second chamber; 5-second conductivity meter.
Detailed Description
The present invention will now be described in detail with reference to the accompanying drawings and examples.
Example 1
Referring to fig. 1, the system for detecting the content of dissolved carbon dioxide in water vapor provided by this embodiment includes a cation exchanger 1, an anion exchanger 2, a carbon dioxide degassing device 4, and a second conductivity meter 5, which are sequentially connected; the cation exchanger 1 is also communicated with a carbon dioxide degassing device 4; the cation exchanger 1 is provided with a water inlet.
In this embodiment, the cation exchanger 1 is an electrically regenerated cation exchanger, which is a commercially available product and mainly functions to remove cations in water by using the principles of electrodialysis and ion migration.
In this embodiment, the anion exchanger 2 is an electrically regenerated anion exchanger, which is a commercially available product and mainly functions to remove anions in water by using the principles of electrodialysis and ion migration.
The carbon dioxide degassing device 4 provided in the present embodiment includes a housing 41 and a degassing membrane 42 disposed on a cross section of the housing 41; degassing membrane 42 divides housing 41 into a first chamber 43 and a second chamber 44; the first chamber 43 communicates with the cation exchanger 1; the second chamber 44 communicates with the anion exchanger 2 and the second conductivity meter 5, respectively.
Referring to fig. 2, the housing 41 has a rectangular configuration, and a degassing membrane 42 is disposed on a cross section of the housing 41 and divides the housing 41 into a first chamber 43 and a second chamber 44 in an upper and lower configuration.
In this embodiment, degassing membrane 42 is a carbon dioxide degassing membrane, model ETC-2.5X 8. The carbon dioxide degassing membrane only allows gas molecules to permeate through, but not water.
In this embodiment, the first chamber 43 is provided with a sample water inlet and a sample water outlet communicated with the sample water inlet, respectively, and the sample water inlet is communicated with the cation exchanger 1; a pure water inlet and a pure water outlet communicated with the pure water inlet are respectively arranged on the second chamber 44, the pure water inlet is communicated with the anion exchanger 2, the pure water outlet is communicated with the second conductivity meter 5, the anion-containing sample water treated by the cation exchanger 1 enters the first chamber 43, the pure water treated by the cation exchanger 1 and the anion exchanger 2 sequentially enters the second chamber 44, carbon dioxide in the anion-containing sample water enters the second chamber 44 through a carbon dioxide degassing membrane, and the rest sample water is discharged through the sample water outlet; the carbon dioxide is mixed with the pure water in the second chamber 44, enters the second conductivity meter 5 through the pure water outlet, is measured for conductivity, and is discharged.
During implementation, the flow direction of the sample water in the first chamber 43 is opposite to the flow direction of the pure water in the second chamber 44, so that the contact time is prolonged, and carbon dioxide in the sample water in the first chamber 43 can enter the second chamber 44 to the maximum degree to be mixed with the pure water.
In this embodiment, the detection system further comprises a first conductivity meter 3 placed between the anion exchanger 2 and the second chamber 44.
In this embodiment, the detection system further includes a power supply connected to the cation exchanger 1, the anion exchanger 2, the first conductivity meter 3, and the second conductivity meter 5, respectively, and operated by power supplied from the power supply.
Example 2
The method for detecting the content of dissolved carbon dioxide in water vapor provided by the embodiment comprises the following steps:
1) preparing n standard samples with carbon dioxide mass concentrations of C1, C2 and … … Cn respectively;
2) sequentially measuring the conductivity values sigma 1, sigma 2 and … … sigma n corresponding to the n standard samples in the step 1);
3) taking the carbon dioxide mass concentrations C1, C2 and … … Cn of the n groups of data obtained in the step 2) as vertical axes, taking the corresponding conductivity values sigma 1, sigma 2 and … … sigma n as horizontal axes, drawing a standard curve of the carbon dioxide mass concentration and the conductivity, and obtaining a standard curve equation of C-sigma;
4) and (3) carrying out ion exchange and degassing treatment on the water sample to be detected containing the carbon dioxide to obtain pure water containing the carbon dioxide, detecting the conductivity value sigma ' of the pure water containing the carbon dioxide, and substituting the sigma ' into the standard curve equation in the step 3) to obtain the mass concentration C ' of the carbon dioxide in the water sample to be detected.
In this embodiment, the specific processes of the ion exchange and degassing treatment in step 4) are as follows:
4.1) carrying out cation exchange on the water sample to be detected to obtain the water sample to be detected containing anions;
4.2) dividing the water sample to be detected containing anions into two paths, wherein one path of water sample is subjected to anion exchange to obtain pure water and then passes through a degassing membrane; the other path directly passes through a degassing membrane;
4.3) passing the pure water and the water sample to be detected containing anions through the degassing membrane, wherein the pure water and the water sample to be detected containing anions correspondingly pass through the two sides of the degassing membrane respectively, and carbon dioxide in the water sample to be detected containing anions enters the pure water through the degassing membrane to obtain the pure water containing carbon dioxide.
In this example, 11 standard samples containing carbon dioxide at different mass concentrations were prepared. Specifically, 11 parts of pure water with the same volume are taken, and a certain amount of carbon dioxide is dissolved in the pure water so that the mass concentration of the carbon dioxide in the pure water is 10 mu g/L, 20 mu g/L, 30 mu g/L, 40 mu g/L, 50 mu g/L, 60 mu g/L, 70 mu g/L, 80 mu g/L, 90 mu g/L, 100 mu g/L and 110 mu g/L in sequence.
Conductivity values corresponding to the 11 standard samples are respectively detected by a conductivity meter, and the detection results are shown in table 1.
TABLE 1 conductivity values for different concentration standards
| Standard sample numbering | Carbon dioxide concentration C (μ g/L) | Conductivity sigma (mu S/cm) |
| 1 | 10 | 0.08 |
| 2 | 20 | 0.12 |
| 3 | 30 | 0.155 |
| 4 | 40 | 0.19 |
| 5 | 50 | 0.215 |
| 6 | 60 | 0.24 |
| 7 | 70 | 0.27 |
| 8 | 80 | 0.285 |
| 9 | 90 | 0.305 |
| 10 | 100 | 0.325 |
| 11 | 110 | 0.345 |
The 11 sets of data in Table 1 were plotted with the conductivity σ on the horizontal axis and the carbon dioxide concentration C on the vertical axis, as shown in FIG. 3.
Further, the curve of fig. 3 is regressed to obtain a relation equation between the carbon dioxide concentration C and the electrical conductivity σ, that is, the standard curve equation is that C is 559.8 σ 3 +308.8σ 2 +162.2 σ -5.07, degree of correlation R 2 ＝0.999。
When the content of the dissolved carbon dioxide in the water vapor system of the power station needs to be detected, a water sample to be detected firstly enters the cation exchanger 1 through the water inlet, the cation in the water sample to be detected is removed by the electrically regenerated cation exchanger, and a water sample only containing anions is obtained, wherein the anions comprise dissolved carbon dioxide and other anions in the water sample, and the dissolved carbon dioxide exists in the form of carbonate and bicarbonate radical in the water sample.
The treated water sample containing anions is divided into two paths, one path of water is further subjected to anion removal through the anion exchanger 2 to obtain pure water, the pure water is subjected to the conductivity measurement of the pure water through the first conductivity meter 3 and then enters the second chamber 44 of the carbon dioxide degassing device 4, the water sample containing further anions is passed directly into the first chamber 43 of the carbon dioxide degasser 4, because the degassing membrane 42 is arranged between the first chamber 43 and the second chamber 44, dissolved carbon dioxide in a water sample containing anions in the first chamber 43 enters the second chamber 44 through the degassing membrane 42, the dissolved carbon dioxide is mixed with pure water to obtain pure water containing carbon dioxide, after flowing out of the second chamber 44, the carbon dioxide-containing pure water is discharged after the conductivity value σ' of the carbon dioxide-containing pure water is detected by the second conductivity meter 5, and the sample water to be measured remaining in the first chamber 43 is discharged from the first chamber 43.
And calculating to obtain the dissolved carbon dioxide content C' in the water sample to be detected according to the obtained standard curve equation of the carbon dioxide concentration C and the conductivity sigma.
During implementation, the content C' of the dissolved carbon dioxide in the water sample to be detected can be calculated manually, a programmable control device can be added in the detection system, the obtained standard curve equation is integrated in the programmable control device, the programmable control device is electrically connected with the second conductivity meter, the detected conductivity signal of the water sample to be detected is directly transmitted to the programmable control device, the content of the dissolved carbon dioxide in the water sample to be detected is directly calculated, and the automation degree is higher.
The detection system provided by the invention can be integrated with a power station water vapor system when in use, realizes the online detection of dissolved carbon dioxide, and is more convenient to operate.
According to the method for detecting the content of dissolved carbon dioxide in water vapor, the trace carbon dioxide is detected by utilizing the electric regeneration ion exchange principle and the carbon dioxide degassing membrane; the whole detection process has high automation degree, and does not need to use any acid solution and alkali solution chemical reagent, thereby avoiding other impurity components from being brought into the detection process.
Claims (10)
1. A method for detecting the content of dissolved carbon dioxide in water vapor is characterized by comprising the following steps:
1) preparing n standard samples with carbon dioxide mass concentrations of C1, C2 and … … Cn respectively;
2) sequentially measuring the conductivity values sigma 1, sigma 2 and … … sigma n corresponding to the n standard samples in the step 1);
3) taking the carbon dioxide mass concentrations C1, C2 and … … Cn of the n groups of data obtained in the step 2) as vertical axes and the corresponding conductivity values sigma 1, sigma 2 and … … sigma n as horizontal axes, drawing a standard curve of the carbon dioxide mass concentration and the conductivity to obtain a standard curve equation of C559.8 sigma 3 +308.8σ 2 +162.2σ-5.07；
4) And (3) carrying out ion exchange and degassing treatment on the water sample to be detected containing the carbon dioxide to obtain pure water containing the carbon dioxide, detecting the conductivity value sigma ' of the pure water containing the carbon dioxide, and substituting the sigma ' into the standard curve equation in the step 3) to obtain the mass concentration C ' of the carbon dioxide in the water sample to be detected.
2. The method for detecting the content of dissolved carbon dioxide in water vapor according to claim 1, wherein the specific processes of ion exchange and degassing treatment in the step 4) are as follows:
4.1) carrying out cation exchange on the water sample to be detected to obtain the water sample to be detected containing anions;
4.2) dividing the water sample to be detected containing anions into two paths, wherein one path of water sample is subjected to anion exchange to obtain pure water and then passes through a degassing membrane; the other path directly passes through a degassing membrane;
4.3) passing the pure water and the water sample to be detected containing anions through a degassing membrane to obtain the pure water containing carbon dioxide.
3. The method for detecting the content of dissolved carbon dioxide in water vapor according to claim 2, wherein in the step 4.3), pure water and the water sample to be detected containing anions correspondingly pass through two sides of the degassing membrane respectively, and carbon dioxide in the water sample to be detected containing anions enters the pure water through the degassing membrane to obtain pure water containing carbon dioxide.
4. A detection system for implementing the method for detecting the content of dissolved carbon dioxide in water vapor according to claim 3, wherein the detection system comprises a cation exchanger (1), an anion exchanger (2), a carbon dioxide degasser (4) and a second conductivity meter (5) which are sequentially communicated; the cation exchanger (1) is also communicated with a carbon dioxide degassing device (4).
5. Detection system according to claim 4, characterised in that the carbon dioxide degassing device (4) comprises a housing (41) and a degassing membrane (42) placed on a cross section of the housing (41); the degassing membrane (42) dividing the housing (41) into a first chamber (43) and a second chamber (44); said first chamber (43) being in communication with a cation exchanger (1); the second chamber (44) is in communication with the anion exchanger (2) and the second conductivity meter (5), respectively.
6. A detection system according to claim 5, wherein the cation exchanger (1) is an electrically regenerated cation exchanger.
7. A detection system according to claim 6, wherein the anion exchanger (2) is an electrically regenerated anion exchanger.
8. A detection system according to claim 7, wherein the degassing membrane (42) is a carbon dioxide degassing membrane.
9. A detection system according to claim 8, characterized in that it further comprises a first conductivity meter (3) interposed between the anion exchanger (2) and the second chamber (44).
10. A detection system according to claim 9, characterized in that the detection system further comprises a power supply connected to the cation exchanger (1), the anion exchanger (2), the first conductivity meter (3) and the second conductivity meter (5), respectively.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115343536A (en) * | 2022-08-23 | 2022-11-15 | 浙江西热利华智能传感技术有限公司 | Power station water vapor multi-parameter cooperative measurement system and method |
| CN115572020A (en) * | 2022-11-09 | 2023-01-06 | 自然资源部第二海洋研究所 | Automatic monitoring device for dissolved inorganic carbon in sewage treatment |
| 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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2022
- 2022-04-29 CN CN202210465475.2A patent/CN114910518A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115343536A (en) * | 2022-08-23 | 2022-11-15 | 浙江西热利华智能传感技术有限公司 | Power station water vapor multi-parameter cooperative measurement system and method |
| 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 |
| CN115572020A (en) * | 2022-11-09 | 2023-01-06 | 自然资源部第二海洋研究所 | Automatic monitoring device for dissolved inorganic carbon in sewage treatment |
| CN115572020B (en) * | 2022-11-09 | 2023-03-07 | 自然资源部第二海洋研究所 | Automatic monitoring device for dissolved inorganic carbon in sewage treatment |
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