CN102012404A - Method for measuring trace chloride ions in methanol - Google Patents
Method for measuring trace chloride ions in methanol Download PDFInfo
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- CN102012404A CN102012404A CN201010218299XA CN201010218299A CN102012404A CN 102012404 A CN102012404 A CN 102012404A CN 201010218299X A CN201010218299X A CN 201010218299XA CN 201010218299 A CN201010218299 A CN 201010218299A CN 102012404 A CN102012404 A CN 102012404A
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- deionized water
- methyl alcohol
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Abstract
The invention relates to the field of analysis and measurement of trace ions in the methanol industry, in particular to a method for measuring trace chloride ions in methanol. The method comprises the steps of: firstly, preparing an elution stock solution, an elution working solution, a sodium chloride standard stock solution and a chloride ion standard working solution from deionized water for later use, then adding an elution solution into a methanol sample and evaporating to dryness, removing organic matters, concentrating and metering volume, finally taking the treated methanol sample, measuring the chloride ions in the methanol through an ion chromatograph, and carrying out data processing and analysis. The invention can accurately analyze chlorides above 10ppb in a methanol product and determine whether to provide the methanol product to a high-end user according to the content so as to increase stable high-end user sources and client satisfaction degrees for enterprises.
Description
Affiliated technical field
The present invention relates to methyl alcohol industry micro ion assay determination field, particularly trace chlorine assay method in the methyl alcohol.
Background technology
Along with the continuous increase of methyl alcohol production capacity, the client is more and more stricter to the requirement of methanol quality, and except that the Interventions Requested that national standard requires, the part high-end user has also proposed requirement to chloride ion content in the methyl alcohol.Because GB does not require chloride ion content in the methyl alcohol, so the present analytical approach of clearly not stipulating.Traditional analytical approach has turbidimetry, electrode potential method, titrimetry etc., measurement range mostly more than 1mg/L, argentometry scope 5-500mg/L for example, mercurimetry scope 1-100mg/L, ion selective electrode method 9-1000mg/L, potentiometric titration detects lower limit 10
-4Mol/L (3.45mg/L) etc.But because the chlorion in the methyl alcohol is microcomponent, and matrix is organism methyl alcohol, adopts said method normally not analyze and error is big, poor reproducibility.
The chromatography of ions has application in recent years in water analysis, detect lower limit 0.2ug/L, can reach the detection requirement, and chlorion does not also have relevant corresponding method in the organism (methyl alcohol) but measure.
Summary of the invention
The objective of the invention is to overcome problems of the prior art, solve the mensuration problem of micro-chlorine in the organism (methyl alcohol), just sample is carried out early stage and handle, eliminate organism, and sample carried out concentration, thereby provide trace chlorine assay method in a kind of methyl alcohol.
Technical scheme of the present invention is as follows:
A, employing deionized water preparation drip washing storing solution, leacheate use liquid, sodium chloride standard reserving solution and chlorion standard to use liquid standby;
B, adopt and to add leacheate in the methyl alcohol sample and be evaporated to driedly, remove organic matter, concentrate and constant volume;
C, get the methyl alcohol sample after the processing, measure chlorion in the methyl alcohol by ion chromatograph.
Described drip washing storing solution, be with the pure sodium carbonate of top grade, sodium bicarbonate behind baking 2h under 105 ℃ of conditions, be dissolved in the deionized water, it is formulated to add deionized water again;
It is that the drip washing storing solution is formulated with 100 times of deionized water dilutions that described leacheate uses liquid;
Described sodium chloride standard reserving solution, be with the top grade pure sodium chloride behind oven dry 2h under 105 ℃ of conditions, be dissolved in the deionized water, add 1/100 drip washing storing solution of total volume, it is formulated to add deionized water again; Described chlorion standard is used liquid, is 1/100 the sodium chloride standard reserving solution of getting total volume, adds 1/100 drip washing storing solution of total volume, and it is formulated to add deionized water again, and ion concentration to be measured is approaching in its concentration and the methyl alcohol.
Chromatographic column adopting YSA-8 anion chromatographic column in the described ion chromatograph.
Described deionized water, all with ultrasound wave degasification in advance, its conductivity is less than 0.5us/cm.
Beneficial effect of the present invention
1, correlativity of the present invention is good, precision is high, r＞0.9990, and accuracy is good, and is easy and simple to handle, is particularly useful for the mensuration of gross sample.
2, the present invention can accurately measure to 10-100ppb, method sensitivity, accurate and favorable reproducibility.
3, the present invention accurately analyzes the above chloride of 10ppb in the methanol product, and chloride ion content in the analytic sample determines whether to offer high-end user according to content simultaneously as required, for enterprise increases stable high-end user source and customer satisfaction.
Description of drawings
Fig. 1 is the chromatography of ions spectrogram of standard model.
Fig. 2 is the chromatography of ions spectrogram of testing sample.
Fig. 3 is the chromatography of ions spectrogram that mark-on reclaims experiment.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing and specific embodiment.
Drip washing storing solution preparation: with the pure sodium carbonate of top grade, sodium bicarbonate behind baking 2h under 105 ℃ of conditions, take by weighing 19.078g sodium carbonate and 14.282g sodium bicarbonate, be dissolved in deionized water, move in the 1000mL volumetric flask, be diluted to graticule with deionized water, filter, be stored in the vinyon bottle, in refrigerator, preserve.
Leacheate uses the liquid preparation: 20.00mL drip washing storing solution is directly pipetted in the 2000mL volumetric flask, be diluted to graticule with deionized water, shake up and be stored in the vinyon bottle, this solution concentration of sodium carbonate is 0.0018mol/L, and sodium bicarbonate concentration is 0.0017mol/L.
Sodium chloride standard reserving solution preparation: the top grade pure sodium chloride 1.6485g that takes by weighing oven dry 2h under 105 ℃ of conditions, be dissolved in deionized water, move in the 1000mL volumetric flask, add 10.00mL drip washing storing solution, be diluted to graticule with deionized water, be stored in the vinyon bottle, preserve in refrigerator, this solution contains the 1.000mg chlorion for every milliliter.
The chlorion standard is used the liquid preparation: preparation contains the standard use liquid of chlorine 10.0ug/mL, draw 10.0mL sodium chloride standard reserving solution in the 1000mL volumetric flask, add 10.0mL drip washing storing solution, be diluted to graticule with deionized water, be stored in the vinyon bottle, preserve in refrigerator, ion concentration to be measured is approaching in its concentration and the methyl alcohol.
The key instrument that adopts is a CIC-100 type ion chromatograph, tool anion separation column and negative ion guard column, regenerate electricity draw up device, computer data processing system, processor for ultrasonic wave certainly.
Condition determination is:
Range: 1; Flow: 1.4ml/min; Electric current: 81mA; Pressure: 4.0MPa.
The analysis of standard model:
Press the solution compound method in the embodiment, prepare drip washing storing solution, drip washing use liquid, sodium chloride standard reserving solution, standard use liquid.
According to the ion chromatograph operation steps, start successively, instrument is online, parameter etc. is set.After regulating, instrument parameter gets final product turn on pump.At first use the deionized water rinsing instrument circuit portion of the degassing about 15 minutes.Close pump then and change leacheate, turn on pump.With Current Regulation to about the 50mA.Gather baseline after 15 minutes, if baseline is steady, and baseline stability just can have been analyzed with interior at 100mv.
Determining and demarcation of standard point: behind instrument stabilizer, analyze (its concentration and sample are approaching) with joining standard use liquid sample introduction.In concrete experiment, select the single point correction method for use.Continuous sample introduction three times, the stable spectrogram that can carry out of peak shape area is handled, and after the spectrogram processing finishes, clicks the quantivative approach key.Select the normalizing key, the counter in the click tools hurdle.Click quantitative component key, clicking goes bail for stays time key, fills in component title and concentration then successively.Click the quantivative approach key.Select calculation correction factor key, the counter in the click tools hurdle.Click quantitative component key, click and get the correction factor key, preservation gets final product then.The spectrogram of standard model is seen accompanying drawing 1.
Standard model (0.1mg/L CL
-) analysis data such as following table:
The analytic record of table 1 standard specimen
| Filename | Sample injection time | Retention time | Peak area |
| Standard specimen (0.1mg/L) | 2007.06.11，10:33:02 | 2.055 | 95915 |
| Standard specimen (0.1mg/L) | 2007.06.11，10:06:06 | 2.050 | 95884 |
| Standard specimen (0.1mg/L) | 2007.06.11，10:11:21 | 2.065 | 96799 |
| Standard specimen (0.1mg/L) | 2007.06.11，10:16:55 | 2.053 | 95607 |
| Standard specimen (0.1mg/L) | 2007.06.11，10:22:41 | 2.041 | 94125 |
| Standard specimen (0.1mg/L) | 2007.06.11，10:27:35 | 2.058 | 97424 |
| Mean value | 2.054 | 95959 | |
| Standard deviation | 0.008 | 1127 | |
| Relative standard deviation % | 0.40 | 1.17 |
Owing to be standard model, be used for doing standard point and determine that this sample introduction advances six times altogether, draws correction factor f=standard specimen content/average peak area=1.04259e-006.Mensuration precision is better, and the peak area relative standard deviation is 1.17%.
The analysis of methyl alcohol sample:
Press the solution compound method in the embodiment, prepare drip washing storing solution, drip washing use liquid, sodium chloride standard reserving solution, use liquid.
Carry out the processing of sample by summary of the invention: sample thief methyl alcohol 100ml adds 10-20ml drip washing and uses liquid in evaporating dish, is evaporated to the basic evaporate to dryness of methyl alcohol in 70 ℃ of water-baths.Be transferred in the volumetric flask of 100ml, it is standby to use liquid to be diluted to the scale mixing with leacheate.
According to the ion chromatograph operation steps, start successively, instrument is online, parameter etc. is set.After regulating, instrument parameter gets final product turn on pump.At first the ultrapure water with the degassing washed the instrument circuit portion about 15 minutes.Close pump then and change leacheate, turn on pump.With Current Regulation to about the 50mA.Gather baseline after 15 minutes, if baseline is steady, and baseline stability just can have been analyzed with interior at 100mv.
Make the sample introduction valve handle be in sample introduction (load) position, with syringe sample is injected into, sample size should be not less than 1ml, then the sample introduction valve handle is pulled to analyzing (inject) position.So just finished the single injected sampling process.(at first use washed with de-ionized water sampling valve 3-5 time before the sample introduction analysis, and then clean sampling valve 3-5 time with sample, workstation should be in state to be analyzed before the sample introduction analysis)
After the spectrogram collection of sample finishes, handle spectrogram.Click the quantivative approach key and choose single point correction.Counter in the click tools hurdle is clicked the quantitative result key then, just can obtain analysis result.(display result, need be revised the result according to the concentration rate difference for concentrating the back sample result).The analysis of spectra of sample is seen accompanying drawing 2 after treatment.
The analysis data such as the following table of methyl alcohol sample:
Table 2 methyl alcohol sample analysis record
| Filename | Sample injection time | Retention time | Peak area | Content (mg/L) |
| Sample introduction for the first time | 2007.06.11，15:17:04 | 2.036 | 47953 | 0.050 |
| Sample introduction for the second time | 2007.06.11，14:57:30 | 2.038 | 48088 | 0.050 |
| Sample introduction for the third time | 2007.06.11，15:03:34 | 2.045 | 48724 | 0.051 |
| Mean value | 2.040 | 48255 | ||
| Standard deviation | 0.004 | 336 | ||
| Relative standard deviation % | 0.19 | 0.7 | ||
| Sample result | 2.040 | 48255 | 0.050 |
Embodiment 3
Sample+standard specimen (doing the mark-on recovery test):
Press the solution compound method in the embodiment, prepare drip washing storing solution, drip washing use liquid, sodium chloride standard reserving solution, working fluid.
Carry out the processing of sample by summary of the invention: sample thief methyl alcohol 100ml adds 10-20ml drip washing and uses liquid in evaporating dish, adds the 0.05mg standard specimen simultaneously, is evaporated to the basic evaporate to dryness of methyl alcohol 70 ℃ of water-baths.Be transferred in the volumetric flask of 100ml, it is standby to use liquid to be diluted to the scale mixing with leacheate.Make the sample introduction valve handle be in sample introduction (load) position, with syringe sample is injected into, sample size should be not less than 1ml, then the sample introduction valve handle is pulled to analyzing (inject) position, finishes the single injected sampling process.(at first use washed with de-ionized water sampling valve 3-5 time before the sample introduction analysis, and then clean sampling valve 3-5 with sample, workstation should be in state to be analyzed before the sample introduction analysis)
After the spectrogram collection of sample finishes, handle spectrogram.Click the quantivative approach key and choose single point correction.Counter in the click tools hurdle is clicked the quantitative result key then, obtains analysis result.(display result, need be revised the result according to the concentration rate difference for concentrating the back sample result).Sample adds 0.05mg CL
-Analysis of spectra behind the standard model is seen accompanying drawing 3.
The analysis data such as the following table of methyl alcohol sample+0.05mg standard specimen:
Table 3 sample+standard specimen analytic record
| Filename | Sample injection time | Retention time | Concentration | Correction factor | Peak area |
| Sample+0.05 standard specimen | 2007.06.11，16:12:26 | 2.052 | 0.099162 | 1.04259e-006 | 95111 |
| Sample+0.05 standard specimen | 2007.06.11，15:50:09 | 2.045 | 0.100523 | 1.04259e-006 | 96417 |
| Sample+0.05 standard specimen | 2007.06.11，15:55:37 | 2.042 | 0.102293 | 1.04259e-006 | 98114 |
| Mean intensity value | 0.100659 |
Reclaim experiment from mark-on and can calculate recovery of standard addition:
Theoretical content * 100% of sample detection content/mark-on sample behind recovery of standard addition=mark-on
From recovery of standard addition experiment and the relative standard deviation data analyzed, with chlorion sensitivity in the ion-chromatographic determination methyl alcohol, accurately and repeatability good, simple and practical.The relative standard deviation of standard specimen and sample determination (RSD) is respectively; 1.17%, 0.7%, the average recovery rate that the sample mark-on is measured shows that 100.0% this method accuracy and repeatability all reach higher level, and measurement result accurately and reliably.
Claims (3)
1. trace chlorine assay method in the methyl alcohol is characterized in that, may further comprise the steps:
A, employing deionized water preparation drip washing storing solution, leacheate use liquid, sodium chloride standard reserving solution and chlorion standard to use liquid standby;
B, adopt and to add leacheate in the methyl alcohol sample and be evaporated to driedly, remove organic matter, concentrate and constant volume;
C, get the methyl alcohol sample after the processing, measure chlorion in the methyl alcohol by ion chromatograph.
Described drip washing storing solution, be with the pure sodium carbonate of top grade, sodium bicarbonate behind baking 2h under 105 ℃ of conditions, be dissolved in the deionized water, it is formulated to add deionized water again;
It is that the drip washing storing solution is formulated with 100 times of deionized water dilutions that described leacheate uses liquid;
Described sodium chloride standard reserving solution, be with the top grade pure sodium chloride behind oven dry 2h under 105 ℃ of conditions, be dissolved in the deionized water, add 1/100 drip washing storing solution of total volume, it is formulated to add deionized water again; Described chlorion standard is used liquid, is 1/100 the sodium chloride standard reserving solution of getting total volume, adds 1/100 drip washing storing solution of total volume, and it is formulated to add deionized water again, and ion concentration to be measured is approaching in its concentration and the methyl alcohol.
2. trace chlorine assay method in the methyl alcohol according to claim 1 is characterized in that, chromatographic column adopting YSA-8 anion chromatographic column in the described ion chromatograph.
3. trace chlorine assay method in the methyl alcohol according to claim 1 is characterized in that, described deionized water, and its conductivity is less than 0.5us/cm, and solutions employed is all prepared with degassed water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010218299 CN102012404B (en) | 2010-07-02 | 2010-07-02 | Method for measuring trace chloride ions in methanol |
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|---|---|---|---|
| CN 201010218299 CN102012404B (en) | 2010-07-02 | 2010-07-02 | Method for measuring trace chloride ions in methanol |
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| CN102012404B CN102012404B (en) | 2013-02-13 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969378A (en) * | 2014-04-14 | 2014-08-06 | 北京工业大学 | Ion chromatography method for detecting conventional ions |
| CN106226454A (en) * | 2016-08-06 | 2016-12-14 | 青岛农业大学 | A kind of measure the ion chromatographic method of trace chloro ion in trimethyl gallium |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03279858A (en) * | 1990-03-29 | 1991-12-11 | Mitsubishi Petrochem Co Ltd | Detection of trace chlorine ion |
| CN101556231A (en) * | 2009-05-27 | 2009-10-14 | 谱尼测试科技（北京）有限公司 | Ocean air salinity measuring method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3279858B2 (en) * | 1995-02-28 | 2002-04-30 | グローリー工業株式会社 | Paper sorting machine |
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2010
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03279858A (en) * | 1990-03-29 | 1991-12-11 | Mitsubishi Petrochem Co Ltd | Detection of trace chlorine ion |
| CN101556231A (en) * | 2009-05-27 | 2009-10-14 | 谱尼测试科技（北京）有限公司 | Ocean air salinity measuring method |
Non-Patent Citations (1)
| Title |
|---|
| JOSEPH SULLIVAN ET AL.: "Determination of inorganic chlorine species in kraft mill bleach effluents by ion chromatography", 《JOURNAL OF CHROMATOGRAPHY A》, vol. 804, no. 12, 30 April 1998 (1998-04-30) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103969378A (en) * | 2014-04-14 | 2014-08-06 | 北京工业大学 | Ion chromatography method for detecting conventional ions |
| CN106226454A (en) * | 2016-08-06 | 2016-12-14 | 青岛农业大学 | A kind of measure the ion chromatographic method of trace chloro ion in trimethyl gallium |
| CN106226454B (en) * | 2016-08-06 | 2018-06-26 | 青岛农业大学 | The ion chromatographic method of trace chloro ion in a kind of measure trimethyl gallium |
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