CN102253142B - Method for determining coexisting impurities and trace arenes in methanol simultaneously - Google Patents
Method for determining coexisting impurities and trace arenes in methanol simultaneously Download PDFInfo
- Publication number
- CN102253142B CN102253142B CN2011101759222A CN201110175922A CN102253142B CN 102253142 B CN102253142 B CN 102253142B CN 2011101759222 A CN2011101759222 A CN 2011101759222A CN 201110175922 A CN201110175922 A CN 201110175922A CN 102253142 B CN102253142 B CN 102253142B
- Authority
- CN
- China
- Prior art keywords
- solution
- methyl alcohol
- xylene
- aromatic hydrocarbons
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention discloses a method for determining coexisting impurities and trace arenes in methanol simultaneously. In the method, gas chromatography is performed on methanol, and an external standard method is used for quantitatively determining the contents of the coexisting impurities and the trace arenes in the methanol, wherein the coexisting impurities refer to methyl acetate, acetone and ethanol, the trace arenes comprise the following components: benzene, toluene, ethylbenzene, p-xylene, m-xylene, o-xylene, styrene and phenol. The coexisting components and the common arenes types in the methanol are considered in the method simultaneously, thus the simultaneous determination method for the eleven components in the methanol is established in an optimization manner. The simultaneous determination of multiple components is beneficial to saving of manpower and material resources to a great extent, acceleration of the detection speed, and accurate judgment of the polluted arenas types in methanol during storage and transportation. The method has the advantages of convenience for operation, low detection cost, accuracy, sensitivity and high efficiency.
Description
Technical field
The present invention relates to the detection method of chemical substance, is a kind of method of simultaneously measuring coexistent impurity and micro-aromatic hydrocarbons in methyl alcohol specifically.
Background technology
Methyl alcohol is of many uses, is basic Organic Chemicals and high-grade fuel.Be mainly used in fine chemistry industry, the fields such as plastics, be used for manufacturing the multiple organic products such as formaldehyde, acetic acid, chloromethanes, first ammonia, dimethyl suflfate, is also one of important source material of agricultural chemicals, medicine.In methyl alcohol, coexisted low-molecular-weight ketone, alcohol, ester class, in methyl alcohol, aromatic hydrocarbons is mainly derived from the pollution of transportation or storage process.Aromatic hydrocarbons can cause acute or slow poisoning to human body, and for relating to the material of safety, health and environmental protection, therefore, aromatic hydrocarbons is limited the quantity of and is put into the pollutant list that China's Environment Priority is controlled.
The aromatic hydrocarbons kind is a lot, common are comprise benzene, toluene, ethylbenzene, dimethylbenzene (comprise to,, o-isomeride), styrene, phenol.Mention and adopt the absorbance curve of photometer scanning methyl alcohol at 190 ~ 350nm about the international methanol production of aromatic hydrocarbons mensuration ，Jin and consumptionn guild (IMPCA) analytical approach in methyl alcohol, check that the line smoothing degree judges whether aromatic hydrocarbons exists.The method is qualitative index, is applicable to the methyl alcohol mensuration that arene content is greater than 10mg/kg, for the curve of 1mg/kg aromatic hydrocarbons especially toluene and dimethylbenzene is very difficult, judges.In methyl alcohol, acetone and ethanol adopt respectively turbidimetry and vapor-phase chromatography.Along with the raising of international methyl alcohol customer requirements, the qualitative and polycomponent Simultaneous Determination of aromatic hydrocarbons kind has become trend.In international trade at present, common aromatic hydrocarbons total amount is limited the quantity of and required as being not more than 1.0mg/kg, prior art can not meet the test request of methanol quality.
Summary of the invention
Goal of the invention: in order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of method of simultaneously measuring coexistent impurity and micro-aromatic hydrocarbons in methyl alcohol.
Technical scheme: in order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of coexistent impurity in methyl alcohol and method of micro-aromatic hydrocarbons simultaneously measured, methyl alcohol is carried out to gas chromatographic analysis, with the coexistent impurity in external standard method quantitative measurement methyl alcohol and the content of micro-aromatic hydrocarbons, wherein coexistent impurity is methyl acetate, acetone, ethanol, and micro-aromatic hydrocarbons comprises following each component: benzene, toluene, ethylbenzene, P-xylene, m-xylene, o-xylene, styrene and phenol.
The concrete steps of said method are as follows:
(1) series standard solution preparation: according to the control requirement of coexistent impurity content range and micro-arene content in methyl alcohol, the mixing series standard solution of preparation appropriate level;
(2) qualitative analysis: under identical chromatogram condition of work, utilize each component standard items retention time and specimen to compare and confirmed;
(3) external standard method equation of linear regression and detect lower limit and determine: serial mixed standard solution is measured, according to chromatographic peak area, utilized external standard method to calculate each component equation of linear regression, and determine the lower limit that detects of each component by 3 times of signal to noise ratio (S/N ratio)s;
(4) precision and recovery test: with component concentration in methyl alcohol sample to be tested, do the background benchmark, add quantitative mixed standard solution in the methyl alcohol sample, under identical chromatographic conditions, continuous several times is measured, the precision of computing method (RSD means with relative standard deviation) and the recovery;
(5) sample determination: directly draw the methyl alcohol sample, measured by identical chromatogram condition of work, according to quantitative each component concentration of the equation of linear regression of peak area and external standard method.
Beneficial effect: compared with prior art, the present invention considers Coexisting component and common aromatic hydrocarbons kind in methyl alcohol simultaneously, optimizes and has set up the Simultaneous Detection of 11 kinds of components in methyl alcohol.Multi-component mensuration simultaneously can be saved the man power and material greatly, can accelerate detection speed, and can accurately judge that methyl alcohol stores and the aromatic hydrocarbons contamination class of transportation.Have easy to operate, testing cost is low, accurate, sensitive, efficient advantage.
The accompanying drawing explanation
Fig. 1 is that in the present invention, each aromatic component is 1.0mg/kg, the chromatogram of the mixed standard solution that each coexistent impurity is 10.0mg/kg.
Embodiment
Below in conjunction with accompanying drawing, technical solution of the present invention is elaborated, but protection scope of the present invention is not limited to described embodiment.
The present invention is a kind of measures the method for coexistent impurity and micro-aromatic hydrocarbons in methyl alcohol simultaneously, it is to adopt vapor-phase chromatography to be analyzed methyl alcohol, with the coexistent impurity in external standard method quantitative measurement methyl alcohol and the content of micro-aromatic hydrocarbons, wherein coexistent impurity is methyl acetate, acetone, ethanol, and micro-aromatic hydrocarbons comprises following each component: benzene, toluene, ethylbenzene, P-xylene, m-xylene, o-xylene, styrene and phenol.
Concrete steps are as follows:
1, serial mixed standard solution preparation:
(11) hybrid standard mother liquor: add respectively benzene, toluene, ethylbenzene, P-xylene in the 100mL volumetric flask, m-xylene, o-xylene, styrene, each 0.100g of phenol, each 1.000g of acetone, methyl acetate and ethanol, use the benchmark methanol constant volume, mix, benzene, toluene, ethylbenzene, P-xylene in the solution obtained, the content of m-xylene, o-xylene, styrene, phenol is 1.00g/L, and acetone, methyl acetate and ethanol content are 10.00g/L;
(12) dilution hybrid standard mother liquor: accurately draw 1.00mL hybrid standard mother liquor in the 100mL volumetric flask with transfer pipet, use the benchmark methanol constant volume, in the solution obtained, the content of each aromatic hydrocarbons is 10mg/L, and the content of each coexistent impurity is 100mg/L;
(13) serial mixed standard solution: draw respectively solution 2.00 mL, 4.00 mL, 6.00 mL, 10.00mL described in step (12) in 4 50mL volumetric flasks, then use respectively the benchmark methanol constant volume, obtain A solution, B solution, C solution, D solution; The 50mL methanol quality is in 39.6g, the content of each aromatic hydrocarbons in A solution, B solution, C solution, D solution is respectively 0.5 mg/kg, 1.0 mg/kg, 1.5 mg/kg, 2.5mg/kg, and the content of each coexistent impurity in A solution, B solution, C solution, D solution is respectively 5.0 mg/kg, 10.0 mg/kg, 15.1 mg/kg, 25.2mg/kg;
2, gas chromatography condition of work:
Detecting device: hydrogen flame detector;
Chromatographic column: INNOWAX chromatographic column (60m * 0.32mm * 0.5 μ m);
Injector temperature: 250 ℃;
Detector temperature: 250 ℃;
Carrier gas (high-purity helium, the purity of helium is greater than 99.99%) flow velocity: 2.0mL/min;
Temperature programme: 60 ℃ keep 4min, are warming up to 120 ℃ with 10 ℃/min and keep 1min, then be warming up to 200 ℃ of maintenance 7min with 20 ℃/min.
Sample size: 1.0 μ L, split sampling, split ratio 10:1.
The chromatogram of mixed standard solution under this chromatogram condition of work (wherein each component concentration of aromatic hydrocarbons is 1.0mg/kg, and each content of coexistent impurity is 10.0mg/kg) is shown in Fig. 1;
Each mark in Fig. 1 is respectively: 1-acetone, 2-methyl acetate, 3-methyl alcohol, 4-ethanol, 5-benzene, 6-toluene, 7-ethylbenzene, 8-P-xylene, 9-m-xylene, 10-o-xylene, 11-styrene, 12-phenol.
3, external standard method equation of linear regression and detect lower limit test: serial mixed standard solution is measured, according to chromatographic peak area, calculated each component external standard method equation of linear regression, and determine the lower limit that detects of each component by 3 times of signal to noise ratio (S/N ratio)s.
4, precision and recovery test: do the background benchmark with component concentration in the methyl alcohol sample to be tested of separate sources, in the methyl alcohol sample, add quantitative mixed standard solution.Under identical chromatographic conditions, follow-on test is 7 times, the test findings reliability is analyzed, and the precision of computing method (RSD means with relative standard deviation) and the recovery, concrete data are in Table 2.
5, sample determination
Under identical chromatographic condition, directly inject 1.0 μ L methyl alcohol samples, measure retention time and the peak area of each component, according to step 2, carry out qualitatively, according to step 3 external standard method regression equation and peak area, to carry out quantitatively, concrete data are in Table 1 and table 2.
The retention time of Coexisting component and aromatic hydrocarbons, external standard method equation of linear regression and detect lower limit in table 1 methyl alcohol
Precision and the recovery test of method when table 2 separate sources methyl alcohol sample is done background
Remarks: 1, the recovery=(total amount average-sample copy floors) * 100/ adds scalar.
2, relative standard deviation RSD is 7 test value statistics gained according to the test total amount.
In the present invention, all reagent is all used the reagent of analyzing pure above purity, and water is three grades of water specifications in GB/T 6682.Benchmark methyl alcohol described in the present invention for analyze pure above methyl alcohol and under described GC conditions coexistent impurity and aromatic hydrocarbons all must not detect.All glasswares are all washed more than 3 times with three grades of ponds, and the parallel repetition of all samples is more than 3 times, and the acquired results relative standard deviation is within 5.0%, to guarantee the accurate of measurement result.
Claims (4)
1. a method of simultaneously measuring coexistent impurity and micro-aromatic hydrocarbons in methyl alcohol, it is characterized in that, methyl alcohol is carried out to gas chromatographic analysis, with the coexistent impurity in external standard method quantitative measurement methyl alcohol and the content of micro-aromatic hydrocarbons, wherein coexistent impurity is methyl acetate, acetone, ethanol, and micro-aromatic hydrocarbons comprises following each component: benzene, toluene, ethylbenzene, P-xylene, m-xylene, o-xylene, styrene and phenol; The concrete steps of the method are as follows:
(1) serial mixed standard solution preparation: according to the control requirement of coexistent impurity content range and micro-arene content in methyl alcohol, the mixing series standard solution of preparation appropriate level;
Wherein series standard solution preparation method is as follows:
(11) hybrid standard mother liquor: add respectively benzene, toluene, ethylbenzene, P-xylene in the 100mL volumetric flask, m-xylene, o-xylene, styrene, each 0.100g of phenol, each 1.000g of acetone, methyl acetate and ethanol, use the benchmark methanol constant volume, mix, benzene, toluene, ethylbenzene, P-xylene in the solution obtained, the content of m-xylene, o-xylene, styrene, phenol is 1.00g/L, and acetone, methyl acetate and ethanol content are 10.00g/L;
(12) dilution hybrid standard mother liquor: accurately draw 1.00mL hybrid standard mother liquor in the 100mL volumetric flask with transfer pipet, use the benchmark methanol constant volume, in the solution obtained, the content of each aromatic hydrocarbons is 10mg/L, and the content of each coexistent impurity is 100mg/L;
(13) serial mixed standard solution: draw respectively solution 2.00mL, 4.00mL, 6.00mL, 10.00mL described in step (12) in 4 50mL volumetric flasks, then use respectively the benchmark methanol constant volume, obtain A solution, B solution, C solution, D solution; The 50mL methanol quality is in 39.6g, the content of each aromatic hydrocarbons in A solution, B solution, C solution, D solution is respectively 0.5mg/kg, 1.0mg/kg, 1.5mg/kg, 2.5mg/kg, and the content of each coexistent impurity in A solution, B solution, C solution, D solution is respectively 5.0mg/kg, 10.0mg/kg, 15.1mg/kg, 25.2mg/kg;
Wherein, benchmark methyl alcohol for analyze pure above methyl alcohol and under described GC conditions coexistent impurity and aromatic hydrocarbons all must not detect;
(2) qualitative analysis: in identical chromatogram condition of work, utilize each component standard items retention time and specimen to compare and confirmed;
(3) external standard method equation of linear regression and detect lower limit and determine: serial mixed standard solution is measured, according to chromatographic peak area, utilized external standard method to calculate each component equation of linear regression, and determine the lower limit that detects of each component by 3 times of signal to noise ratio (S/N ratio)s;
(4) precision and recovery test: with component concentration in methyl alcohol sample to be tested, do the background benchmark, add quantitative mixed standard solution in the methyl alcohol sample, under identical chromatographic conditions, continuous several times is measured, and means precision and the recovery of computing method with relative standard deviation RSD;
(5) sample determination: directly draw the methyl alcohol sample, measured under identical chromatogram condition of work, according to quantitative each component concentration of the equation of linear regression of peak area and external standard method;
GC conditions described in above-mentioned steps (2) and step (5) is: detecting device is hydrogen flame detector; Chromatographic column is the INNOWAX chromatographic column; Injector temperature is 250 ℃; Detector temperature is 250 ℃; Flow rate of carrier gas is 2.0mL/min; Sample size is 1.0 μ L, split sampling, split ratio 10:1; Temperature programme.
2. a kind of method of simultaneously measuring coexistent impurity and micro-aromatic hydrocarbons in methyl alcohol according to claim 1, it is characterized in that, the method of temperature programme is: keep 4min at 60 ℃, be warming up to 120 ℃ with 10 ℃/min and keep 1min, then be warming up to 200 ℃ of maintenance 7min with 20 ℃/min.
3. a kind of method of simultaneously measuring coexistent impurity and micro-aromatic hydrocarbons in methyl alcohol according to claim 1, is characterized in that, the length of described INNOWAX chromatographic column is that 60m, internal diameter are that 0.32mm, thickness are 0.5 μ m.
4. a kind of method of simultaneously measuring coexistent impurity and micro-aromatic hydrocarbons in methyl alcohol according to claim 1, is characterized in that, carrier gas used is helium, and purity is greater than 99.99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101759222A CN102253142B (en) | 2011-06-28 | 2011-06-28 | Method for determining coexisting impurities and trace arenes in methanol simultaneously |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101759222A CN102253142B (en) | 2011-06-28 | 2011-06-28 | Method for determining coexisting impurities and trace arenes in methanol simultaneously |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102253142A CN102253142A (en) | 2011-11-23 |
| CN102253142B true CN102253142B (en) | 2013-12-04 |
Family
ID=44980523
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101759222A Expired - Fee Related CN102253142B (en) | 2011-06-28 | 2011-06-28 | Method for determining coexisting impurities and trace arenes in methanol simultaneously |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102253142B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2491544C1 (en) * | 2012-03-11 | 2013-08-27 | Открытое акционерное общество "ВНИПИгаздобыча" | Method of simultaneous determination of diehtylene glycol and methanol in natural and sewage water by method of liquid chromatography |
| CN102830194A (en) * | 2012-07-06 | 2012-12-19 | 复旦大学 | Method for rapidly detecting residual amount of benzene-based pollutants in plastic particles |
| CN110568085B (en) * | 2018-06-05 | 2021-10-29 | 中国石油化工股份有限公司 | Method for determining acetonitrile content in sample |
| CN109781913B (en) * | 2018-12-07 | 2022-04-01 | 江苏永葆环保科技有限公司 | Method for detecting organic matters in waste acid liquor |
| CN110441458B (en) * | 2019-08-19 | 2021-11-05 | 山东绅联生物科技有限公司 | Gas chromatography analysis method for detecting substances in phthalic anhydride |
| CN110988236A (en) * | 2019-12-03 | 2020-04-10 | 江苏恒信检验有限公司 | Method for detecting benzene, toluene and xylene in ethanol |
| CN112526053A (en) * | 2020-12-29 | 2021-03-19 | 陕西延长石油（集团）有限责任公司 | Method for measuring mixed alcohol and mixed ester in industrial ethanol by gas chromatography internal standard method |
-
2011
- 2011-06-28 CN CN2011101759222A patent/CN102253142B/en not_active Expired - Fee Related
Non-Patent Citations (8)
| Title |
|---|
| 唐洪等.气相色谱法同时测定工作场所中甲醇和苯系物.《中国卫生检验杂质》.2008,第18卷(第2期),289-290、301. |
| 李志宏等.气相色谱法测定甲醇中杂质含量.《中氮肥》.2009,(第4期),59-61. |
| 气相色谱法同时测定工作场所中甲醇和苯系物;唐洪等;《中国卫生检验杂质》;20080229;第18卷(第2期);289-290、301 * |
| 气相色谱法测定甲醇中杂质含量;李志宏等;《中氮肥》;20090731(第4期);59-61 * |
| 王清龙.甲醇中微量杂质的分析.《石油化工》.1987,第16卷(第9期),654-657. |
| 甲醇中微量杂质的分析;王清龙;《石油化工》;19871231;第16卷(第9期);654-657 * |
| 甲醇中杂质分析;闵成勇;《泸天化科技》;20031231(第4期);285-287 * |
| 闵成勇.甲醇中杂质分析.《泸天化科技》.2003,(第4期),285-287. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102253142A (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102253142B (en) | Method for determining coexisting impurities and trace arenes in methanol simultaneously | |
| CN101887051B (en) | Online chromatographic analysis method | |
| CN102331475A (en) | Method for measuring content of phthalate compounds in tipping paper for cigarettes | |
| CN101762653A (en) | Method for determining main phenolic compounds in main stream smoke of cigarette | |
| CN101261255A (en) | Gasoline benzene, oxygen content rapid detection method | |
| CN101887052A (en) | Online chromatographic analysis device | |
| CN104502477B (en) | Organic analytical approach in a kind of trichloroacetaldehyde Waste Sulfuric Acid | |
| CN102445507B (en) | Method for determining vinyl content in methyl vinylsiloxane rubber or silicone oil | |
| CN105021740A (en) | High-performance liquid chromatography analytical method for N1,N1-diisopropyl ethylenediamine | |
| CN103512974B (en) | Method for rapidly determining contents of aureomycin for feed and impurities of aureomycin by HPLC | |
| CN107132287A (en) | The measuring method of trimethylamine in industrial methanol | |
| CN103091410B (en) | Method for measuring phthalate type compound content in reconstituted tobacco | |
| CN103134863A (en) | Method of determining content of methanol, isobutanol, isoamylol of alcohol | |
| CN109324135B (en) | Method for simultaneously detecting 3 emulsifiers in composite emulsifier | |
| CN106770764A (en) | A kind of content assaying method of Xue bijing intermediate multi-target ingredient | |
| CN102749390B (en) | Method for determining contents of microscale allene and acetylene in MTO (methanol to olefin) products through gas chromatography | |
| CN104730156A (en) | Method for detecting benzenes in chromatographic-grade carbon disulfide | |
| CN102435685A (en) | Method for measuring purity of 2-mercaptobenzothiazole by using high performance liquid chromatograph | |
| CN103257117A (en) | Rapid gasoline component measurement system | |
| CN103048407A (en) | Content detection method for lysine of compound ketoacid tablet | |
| CN202903754U (en) | Inlet gas path automatic control structure of flame ionization detector of gas chromatograph | |
| CN104634886B (en) | Method for determining absolute content of organic carboxylic acid | |
| CN102759583B (en) | Assay method of content of aleuritic acid | |
| CN103913524B (en) | The detection method of carbon disulphide and thiophene content in a kind of Simultaneously test coking benzene | |
| CN201716291U (en) | Analyzer for measuring gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131204 Termination date: 20160628 |