CN106442798B - A kind of accurate measuring method of humic-acid kind organic matter high-temperature decomposition product - Google Patents
A kind of accurate measuring method of humic-acid kind organic matter high-temperature decomposition product Download PDFInfo
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- CN106442798B CN106442798B CN201610962722.4A CN201610962722A CN106442798B CN 106442798 B CN106442798 B CN 106442798B CN 201610962722 A CN201610962722 A CN 201610962722A CN 106442798 B CN106442798 B CN 106442798B
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Abstract
The invention discloses a kind of accurate measuring methods of humic-acid kind organic matter high-temperature decomposition product, it is specifically a kind of that Accurate Analysis detection is carried out to humic-acid kind organic matter high-temperature decomposition product in aqueous vapor from power plant system using ion chromatogram eluate Gradient program method, the humic-acid kind organic matter high-temperature decomposition product is mainly low molecular organic acids and aggressivity inorganic anion, specific step is as follows: humic-acid kind organic matter pyrolytic liquid is passed through 0.45 μm of filtering with microporous membrane, after concentrating sample volume, inject in the quantitative sample injection ring of ion chromatograph；The testing conditions of the ion chromatogram eluate Gradient program method are as follows: the column temperature of anion analysis column and guard column is 30 DEG C ± 0.1 DEG C, leacheate K2B4O7Solution, gradient elution, leacheate flowing velocity are controlled in 1.00mL/min, and the current control of suppressor is in 60mA, 500 μ L of sampling volume.Analysis method of the invention, the detection limit of each ion its standard deviation under the premise of guaranteeing minimum is minimum, is suitable for quick, the accurate detection of humic-acid kind organic matter high-temperature decomposition product in aqueous vapor from power plant system.
Description
Technical field
The present invention relates to a kind of accurate measuring method of humic-acid kind organic matter high-temperature decomposition product, specifically a kind of uses
Ion chromatogram eluate Gradient program method carries out humic-acid kind organic matter high-temperature decomposition product in aqueous vapor from power plant system accurate
Analysis detection.
Background technique
With the rapid development of power industry, " condensing turbine heat supply transformation " also rapid proliferation supplies to meet unit
Heat, supply water also increase therewith, and the organic matter that make-up water is brought into also dramatically increases, and humic-acid kind organic matter is a kind of main
Organic matter represent, in thermal power generation therrmodynamic system, humic-acid kind organic matter under high temperature and high pressure environment under decompose, generate
The impurity for seriously affecting water and steam quality and heat power equipment, the low molecular organic acids and impurity being mainly reflected in Water vapour images
Anion-content also gradually increases, and the content of these high-temperature decomposition products is exceeded, not only conductance is severely exceeded, but also heating power
Equipment causes very big threat to safe operation also by different degrees of corrosion impact.Therefore propose that a kind of humic-acid kind has
The accurate measuring method of machine object high-temperature decomposition product is inevitable requirement, and the accuracy of institute's detection data, which is similarly, to be purified water and set
Standby anti-corrosion has important reference value.
The chromatography of ions is a kind of traditional detection method that mid-term the 1970s is born, and is the weight of high performance liquid chromatography
Want branch, be that current zwitterion compounds content detection predominantly detects means, and in the water-steam system of thermal power plant from
There is important application in terms of sub- content detection, become research and handles the powerful tool of power equipment etching problem, but it is conventional
Analytic type ion chromatography is applied in practical power plant runs many defects, firstly, conventional analysis type ion chromatogram eluate stream
Speed is very big, is difficult to accomplish the operation that is continuously switched on, and need the amount of samples of large volume, this keeps large batch of steam detection very limited
System, secondly, steam ingredient becomes relative complex for present therrmodynamic system, humic-acid kind organic matter high-temperature decomposition product is same
When there are low molecular organic acids and inorganic anion, for these complicated samples because variety classes ion pair it is common from
The affinity of sub- chromatographic column fixed phase is difficult to find suitable leacheate type and concentration and separates them there are larger difference,
It is be easy to cause detection error, therefore, it is necessary to method improvement is carried out in original conventional analysis type ion chromatographic method.
A kind of accurate measuring method of humic-acid kind organic matter high-temperature decomposition product proposed by the present invention, it is specifically a kind of to adopt
Essence is carried out to humic-acid kind organic matter high-temperature decomposition product in aqueous vapor from power plant system with ion chromatogram eluate Gradient program method
True analysis detection, it is with strong points, the defect of conventional method can be overcome, it is easy to operate, it works well.
Summary of the invention
The present invention relates to a kind of accurate measuring methods of humic-acid kind organic matter high-temperature decomposition product, in order to make up above-mentioned back
The related defects that scape technology is mentioned, method of the invention is by a kind of ion chromatogram eluate Gradient program method to aqueous vapor from power plant
In system humic-acid kind organic matter high-temperature decomposition product carry out Accurate Analysis detection, and in particular to organic matter high-temperature decomposition product
It is low molecular organic acids based on formic acid and acetic acid and with F-, Cl-, SO4 2-, PO4 3-, NO3 -Based on aggressivity it is inorganic yin from
The measurement of son can be promptly to measure ion concentration using this measuring method in the short time, the detection limit of each ion is guaranteeing most
Its standard deviation is minimum under the premise of low, is suitable for humic-acid kind organic matter high-temperature decomposition product, accurate to detect.
To achieve the above object, main technical schemes adopted by the present invention are as follows:
A kind of accurate measuring method of humic-acid kind organic matter high-temperature decomposition product, which is characterized in that use ion chromatography
Leacheate Gradient program method carries out Accurate Analysis detection to humic-acid kind organic matter high-temperature decomposition product in aqueous vapor from power plant system,
The organic matter high-temperature decomposition product is low molecular organic acids based on formic acid and acetic acid and with F-, Cl-, SO4 2-, PO4 3-,
NO3 -Based on aggressivity inorganic anion, the specific steps are as follows:
Sample to be tested is passed through into 0.45 μm of filtering with microporous membrane, after concentrating sample volume, injects quantifying for ion chromatograph
In injection annulus, the testing conditions of ion chromatogram eluate Gradient program method are as follows: the column temperature of anion analysis column and guard column is 30
DEG C ± 0.1 DEG C, leacheate K2B4O7Solution, gradient elution, leacheate flowing velocity are controlled in 1.00mL/min, suppressor
Current control is in 60mA, 500 μ L of sampling volume.
The leacheate is the K of various concentration gradient2B4O7Solution, the program of gradient elution are as follows: 0 ~ 2min, leacheate
K2B4O7The concentration of solution is 0mmol/L；2 ~ 7min, leacheate K2B4O7The concentration of solution is 0 ~ 4.5mmol/L；7 ~ 21min, leaching
Washing lotion K2B4O7The concentration of solution is 4.5 ~ 25.0mmol/L；21 ~ 30min, leacheate K2B4O7The concentration of solution is 25.0mmol/
L。
The leacheate uses K2B4O7Solution is to overcome traditional leacheate KOH or NaOH vulnerable to CO in air2It is dry
It disturbs.
In conclusion a kind of accurate measurement side of humic-acid kind organic matter high-temperature decomposition product of the present invention
Method accurately surveys humic-acid kind organic matter high-temperature decomposition product using ion chromatogram eluate Gradient program method more particularly to a kind of
Fixed method, the defects of overcoming the chromatographic measurement error of conventional ion big, can decomposed solution described in Accurate Determining in a short time
Component content, be suitable for the measurement of current thermal power plant humic-acid kind organic matter high-temperature decomposition product, it is with strong points, to prison
Water and steam quality is superintended and directed, guarantees that the safe operation of heat power equipment has very important meaning.
Detailed description of the invention
Fig. 1 is the chromatography of ions figure of mixed standard solution, wherein 1.F-10µg/L；2.CH3COO-10µg/L；3.HCOO-5
µg/L；4.Cl-200µg/L；5.NO3 -100µg/L；6.SO4 2-400µg/L；7.PO4 3-60µg/L；
Fig. 2 is the chromatography of ions figure of steam sample detection, wherein 1.F-；2.CH3COO-；3.HCOO-；4.Cl-；5.NO3 -；
6.SO4 2-；7.PO4 3-。
Fig. 3 is the accurate measurement result of humic acid high-temperature decomposition product under various concentration.
Specific embodiment
The method of the present invention is further described through below with reference to embodiment, it is to be noted that, explanation below is only
It is to explain the method for the present invention, does not limit primary bright content.
Example 1: certain in-service Power Plant Water Vapor sample detection
1. instrument and reagent
The instrument that experiment uses is ion chromatograph, anion separation column and to protect all be matched common chromatographic column,
Conductometric detector, sample injector.
Sodium formate, sodium acetate, sodium fluoride, sodium chloride, sodium sulphate, sodium phosphate, sodium nitrate, dipotassium tetraborate, medicine described above
Product are that analysis is pure, configure leacheate K2B4O7Solution (gradient concentration leacheate), the series standard stock solution of each anion are equal
For 1000 μ g/L, above-mentioned seven kinds of standard stock solutions and leacheate are matched with the ultrapure water that resistivity is 18.25M cm
It sets, is stored in polyethylene bottle to be placed in 0 ~ 4 DEG C of environment and store.
2. configuration and the instrument calibration of standard solution
According to the detection sensitivity of the concentration range of taken sample to be tested and each anion, appropriate anion mark is accurately pipetted
Quasi- stock solution dilutes constant volume with ultrapure water, is configured to the hybrid standards of seven kinds of anion using liquid, according to steam sample in this example
The normal concentration that product concentration range determines is CH3COO-10µg/L、HCOO-5µg/L、F-10µg/L、Cl-200µg/L、NO3 -100µ
g/L、PO4 3-60µg/L、SO4 2-The hybrid standard of 400 μ g/L uses liquid.
3. chromatography detects
Sample to be tested is passed through into 0.45 μm of filtering with microporous membrane, after concentrating sample volume, injects quantifying for ion chromatograph
In injection annulus, the testing conditions of ion chromatogram eluate Gradient program method are as follows: the column temperature of anion analysis column and guard column is 30
DEG C ± 0.1 DEG C, leacheate K2B4O7Solution, gradient elution, leacheate flowing velocity are controlled in 1.00mL/min, suppressor
Current control is in 60mA, 500 μ L of sampling volume.
4. gradient elution program
Gradient elution is to change elution intensity by changing the concentration of leacheate in the analysis process, thus primary
Separation while completing to have resin affinity the different ions of larger difference in sample introduction.Therefore, it is desired to which leacheate is by inhibiting
Rear backdrop conductance is low and concentration change after fluctuate it is small；In Gradient program conversion, the system balancing time is short.In view of variety classes
Anionic face is different to its retained fraction separating degree of the leacheate of various concentration, and high concentration leacheate will lead to weak retained fraction
Separating degree is deteriorated, low concentration leacheate then will lead to it is too long between separation, by test of many times, so that it is determined that optimal gradient is drenched
Wash concentration.
The leacheate is the K of various concentration gradient2B4O7Solution, the program of gradient elution are as follows: 0 ~ 2min, leacheate
K2B4O7The concentration of solution is 0mmol/L；2 ~ 7min, leacheate K2B4O7The concentration of solution is 0 ~ 4.5mmol/L；7 ~ 21min, leaching
Washing lotion K2B4O7The concentration of solution is 4.5 ~ 25.0mmol/L；21 ~ 30min, leacheate K2B4O7The concentration of solution is 25.0mmol/
L。
5. spectrum analysis
Standard solution spectrogram and steam sample solution spectrogram are obtained by above 4 steps, as shown in figures 1 and 2.
Example 2: the accurate measurement of humic acid high-temperature decomposition product under various concentration
The operating procedure of examples detailed above 1 is repeated, chooses instrument and reagent, simultaneously configuration standard uses liquid to calibration instrument, to not
Chromatography is carried out with humic acid pyrolytic liquid under concentration, using gradient elution program, is obtained under the decomposition of various concentration humic acid
Product assay result is as shown in table 3 below, and trend chart is as shown in Figure 3, wherein the decomposition concentration gradient setting point of humic acid
It Wei not 0 μ g/L, 1500 μ g/L, 3500 μ g/L, 5500 μ g/L, 7500 μ g/L.
The accurate measurement example of humic acid high-temperature decomposition product illustrates a kind of rotten plant according to the present invention under various concentration
The accurate measuring method of acids organic matter high-temperature decomposition product has application, repeats measurement.
Product assay under the decomposition of 1 various concentration humic acid of table
In conclusion this method completes the accurate measurement of humic-acid kind organic matter high-temperature decomposition product within half an hour,
Gradient elution program has been successively performed elution pillar, balances pillar, enriched sample, and gradient analysis terminates to analyze this five steps,
In 0 ~ 25min, leacheate K2B4O7The concentration of solution rises to 25.0mmol/L from 0mmol/L, then keeps this concentration, directly
To all components to be measured are eluted, weak retained fraction is not only effectively isolated, but also shortens the strong analysis time for retaining ion, reaches fast
Speed is accurately analyzed, this measuring method is with strong points, and feasibility is strong, strong operability, and repeatability is good, is that a kind of completion is rotten
Effective measuring method of phytic acid type organic high-temperature decomposition product.
Claims (2)
1. a kind of accurate measuring method of humic-acid kind organic matter high-temperature decomposition product, which is characterized in that drenched using ion chromatography
Washing lotion Gradient program method carries out Accurate Analysis detection, institute to humic-acid kind organic matter high-temperature decomposition product in aqueous vapor from power plant system
Stating organic matter high-temperature decomposition product is low molecular organic acids based on formic acid and acetic acid and with F-, Cl-, SO4 2-, PO4 3-, NO3 -
Based on aggressivity inorganic anion；The leacheate is K2B4O7Solution, gradient elution；The control of leacheate flowing velocity exists
1.00mL/min；K2B4O7The program of solution gradient elution are as follows: 0~2min, leacheate K2B4O7The concentration of solution is 0mmol/L；2
~7min, leacheate K2B4O7The concentration of solution is 0~4.5mmol/L；7~21min, leacheate K2B4O7The concentration of solution is
4.5~25.0mmol/L；21~30min, leacheate K2B4O7The concentration of solution is 25.0mmol/L.
2. the accurate measuring method of humic-acid kind organic matter high-temperature decomposition product according to claim 1, feature exist
In testing conditions are as follows: the column temperature of anion analysis column and guard column is 30 DEG C ± 0.1 DEG C；The electric current of suppressor: 60mA；Sample introduction
Volume: 500 μ L.
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| CN107436332B (en) * | 2017-08-01 | 2020-05-22 | 清华大学 | Method for separating and measuring components with different polarities and molecular weights of humic acid |
| CN112321030A (en) * | 2020-11-30 | 2021-02-05 | 西安西热控制技术有限公司 | Water vapor treatment process for thermal power plant |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10206404A (en) * | 1997-01-27 | 1998-08-07 | Showa Denko Kk | Analysis method of anion and anion analysis set |
| CN104090039A (en) * | 2014-07-08 | 2014-10-08 | 青海大学 | Method for simultaneously determining inorganic anions and organic acid radical ions in salt lake brine |
| CN104535669A (en) * | 2014-11-27 | 2015-04-22 | 国家电网公司 | Method capable of simultaneous determination of various trace anions in water vapor of thermal power generating unit |
| CN105190306A (en) * | 2013-03-13 | 2015-12-23 | 贝克休斯公司 | Use of detection techniques for contaminant and corrosion control in industrial processes |
| CN105203656A (en) * | 2015-09-14 | 2015-12-30 | 国网山东省电力公司电力科学研究院 | Shandong area insulator dirtiness water-soluble negative ion ingredient testing method |
| CN105784908A (en) * | 2016-04-13 | 2016-07-20 | 广东中烟工业有限责任公司 | Ion chromatography detection method for six negative ions in cigarette paper |
| CN106053627A (en) * | 2016-05-12 | 2016-10-26 | 中华人民共和国日照出入境检验检疫局 | Method for simultaneously detecting 26 organic acids and inorganic negative ions in juice |
-
2016
- 2016-11-04 CN CN201610962722.4A patent/CN106442798B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10206404A (en) * | 1997-01-27 | 1998-08-07 | Showa Denko Kk | Analysis method of anion and anion analysis set |
| CN105190306A (en) * | 2013-03-13 | 2015-12-23 | 贝克休斯公司 | Use of detection techniques for contaminant and corrosion control in industrial processes |
| CN104090039A (en) * | 2014-07-08 | 2014-10-08 | 青海大学 | Method for simultaneously determining inorganic anions and organic acid radical ions in salt lake brine |
| CN104535669A (en) * | 2014-11-27 | 2015-04-22 | 国家电网公司 | Method capable of simultaneous determination of various trace anions in water vapor of thermal power generating unit |
| CN105203656A (en) * | 2015-09-14 | 2015-12-30 | 国网山东省电力公司电力科学研究院 | Shandong area insulator dirtiness water-soluble negative ion ingredient testing method |
| CN105784908A (en) * | 2016-04-13 | 2016-07-20 | 广东中烟工业有限责任公司 | Ion chromatography detection method for six negative ions in cigarette paper |
| CN106053627A (en) * | 2016-05-12 | 2016-10-26 | 中华人民共和国日照出入境检验检疫局 | Method for simultaneously detecting 26 organic acids and inorganic negative ions in juice |
Non-Patent Citations (5)
| Title |
|---|
| Ion chromatography of organic-rich natural waters from peatlands I.Cl-,NO2-,Br-,NO3-,HPO42-,SO42- and oxalate;William Shotyk;《Journal of Chromatography》;19930625;第640卷(第1-2期);第309-316页 * |
| Ion chromatography of organic-rich natural waters from peatlands III. Improvements for measuring anions and cations;Philipp Steinmann 等;《Journal of Chromatography A》;19950707;第706卷(第1-2期);第281-286页 * |
| Simultaneous determination of small organic and inorganic anions in environmental water samples by ion-exchange chromatography;Adrian A.Ammann 等;《Journal of Chromatography A》;19950707;第706卷(第1-2期);第259-269页 * |
| 电厂用阳离子交换树脂高温分解特性研究;荆玲玲 等;《热能动力工程》;20120131;第27卷(第1期);第96-100页 * |
| 离子色谱法测定核电站一回路冷却剂中痕量痕量F-，Cl–和SO42–;韩剑 等;《化学分析计量》;20160731;第25卷(第4期);第64-68页 * |
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