CN103792297A - Chromatography-mass spectrometry method for determining oxygen-containing compounds in complex olefin matrix - Google Patents
Chromatography-mass spectrometry method for determining oxygen-containing compounds in complex olefin matrix Download PDFInfo
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- CN103792297A CN103792297A CN201210429247.6A CN201210429247A CN103792297A CN 103792297 A CN103792297 A CN 103792297A CN 201210429247 A CN201210429247 A CN 201210429247A CN 103792297 A CN103792297 A CN 103792297A
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Abstract
The invention provides a chromatography-mass spectrometry method for determining oxygen-containing compounds in a complex olefin matrix, which adopts a mixture containing oxygen-containing compounds and light hydrocarbons as an analyte, and performs analysis by a gas chromatography-mass spectrometry device; the analyte is introduced from a chromatography split sampling port, is separated by a chromatographic column with extremely strong polarity, is detected by a mass spectrometry device, and is quantified by characteristic ions. The method has the advantages that characteristic ions are used for quantification, and the method is low in separation requirements, comprehensive in analyzed low-carbon aldehyde alcohol ketone oxygen-containing compounds, and accurate in quantification.
Description
Technical field
The present invention relates to a kind of Spectrometry method that in complicated Olefins matrix, oxygenatedchemicals is measured.
Background technology
Light olefin ethene, propylene, isobutylene, 1-butylene etc. are the basic organic of modern chemistry industry, and the traditional handicraft route of preparing ethylene, propylene is naphtha pyrolysis.Take coal or rock gas as raw material through Methanol the new method for the low-carbon alkene such as ethene, propylene, as methanol-to-olefins (Methanol to Olefins, be called for short MTO), preparing propylene from methanol (MTP), ethanol alkene processed (ETO) etc. is be hopeful the new technology of petroleum replacing route most and moving towards the industrialization.The oxygenatedchemicals of low-carbon (LC) as ethers, aldehydes, alcohols and ketone impurity be the large class impurity of another except hydrocarbon impurities in light olefin.Because oxygenatedchemicals impurity directly affects the polymerization of alkene, therefore in light olefin production process and product, all need to measure and control the content of these oxygenatedchemicals impurity.The standard method of measuring at present oxygenatedchemicals impurity in light olefin has GB/T 12701-1990 " the mensuration vapor-phase chromatography of Trace Methanol content in industrial ethene, propylene ", SH/T 1547-2004 " the mensuration vapor-phase chromatography of Trace Methanol and methyl tert-butyl ether in industrial 1-butylene ", SH/T 1483-2004 " the mensuration vapor-phase chromatography of oxygenatedchemicals in industrial isobutylene " etc.
GB/T 12701-1990 " the mensuration vapor-phase chromatography of Trace Methanol content in industrial ethene, propylene " is for measuring the Trace Methanol of ethene and propylene; SH/T 1547-2004 " the mensuration vapor-phase chromatography of Trace Methanol and methyl tert-butyl ether in industrial 1-butylene " is for measuring Trace Methanol and the methyl tertbutyl ether content of 1-butylene.Methyl alcohol and the methyl tertbutyl ether content in light olefin only measured in these two standard methods, do not consider in alkene may some aldoketones impurity as acetaldehyde, propionic aldehyde, butyraldehyde, ethanol, isopropyl alcohol, sec-butyl alcohol, acetone, butanone, 2 pentanone, methyl-n-butyl ketone, 3-hexanone etc.SH/T 1483-2004 " the mensuration vapor-phase chromatography of oxygenatedchemicals in industrial isobutylene ", for measuring micro-dimethyl ether, methyl tertbutyl ether content, acetone and C1 ~ C4 alcohols of isobutylene, does not consider aldehyde type impurities and other ketone impurity.
The component that these standard methods are considered is on the one hand comprehensive not, all belongs to the standard method for the specificity of product on the one hand in addition, lacks a kind of detection method of versatility.The reaction product such as naphtha pyrolysis product or methanol-to-olefins (MTO) is very long through being separated to the process route of olefin product, in product and detachment process, need equally to detect and control oxygenatedchemicals impurity, especially methanol-to-olefins (MTO) and preparing propylene from methanol (MTP) are made raw material with methyl alcohol, in its product, the distribution of low-carbon oxygen-containing compound is wider, almost contained aldehyde, ketone, alcohol, ether, the acids impurity composition of low-carbon (LC).
Summary of the invention
Technical matters to be solved by this invention is to exist separating effect undesirable while utilizing in existing chromatographic process Analysis of Complex Olefins matrix oxygenatedchemicals, analyze component not comprehensive, can not measure the aldehyde type impurities that may exist in alkene and the problem of part alcohol ketone impurity content, a kind of Spectrometry method that in new complicated Olefins matrix, oxygenatedchemicals is measured is provided.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the Spectrometry method that in complicated Olefins matrix, oxygenatedchemicals is measured, take the potpourri that contains oxygenatedchemicals and light hydrocarbons as analyzing material, analyze by gas chromatography-mass spectrum device, described analysis material is by chromatogram split sampling mouth sample introduction, chromatographic column by strong polarity separates, and is then detected by mass detector and is undertaken quantitatively by characteristic ion.
Described chromatographic column is TCEP[1,2,3-tri-(2-cyanoethoxyl)] propane capillary chromatographic column or polyglycol be the capillary chromatographic column of fixing phase.
Described chromatographic column is take helium as carrier gas, and carrier gas flux is 0.5～3.0 ml/min, and temperature is 40～130 ℃.
Described oxygenatedchemicals is selected from: methyl tert-butyl ether, acetaldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, sec-butyl alcohol, 2 pentanone, 3-hexanone.
Described oxygenatedchemicals is selected from: acetaldehyde, propionic aldehyde, butyraldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, 3-methyl-2-butanone, propione, 2 pentanone, 3-methyl-2 pentanone and 3-hexanone.
Described oxygenatedchemicals does not comprise dimethyl ether.
Described analysis material is the reaction product of methanol-to-olefins.
The oxygenatedchemicals of low-carbon (LC) conventionally has certain polarity except ethers, therefore the common chromatographic column that adopts strong polarity of these polarity oxygenatedchemicalss of analyzing in light olefin is polyglycol or TCEP[1 as fixed mutually, 2,3-tri-(2-cyanoethoxyl)] propane capillary chromatographic column.Dimethyl ether is difficult in polar column with light olefin separate a little less than due to the low polarity of boiling point, conventionally need to adopt the chromatographic column of other type.If analytic target is complicated especially light olefin product, while containing some heavier alkane olefin component in light olefin sample, even if adopt TCEP[1,2,3-tri-(2-cyanoethoxyl)] propane capillary chromatographic column, methyl tert-butyl ether, acetaldehyde, propionic aldehyde and butyraldehyde also may cannot separate completely with some alkane alkene.The TCEP[1 of the strong polarity of the inventive method utilization, 2,3-tri-(2-cyanoethoxyl)] propane capillary chromatographic column 2 separates, methyl tert-butyl ether, acetaldehyde, propionic aldehyde and butyraldehyde can not separate completely with some alkane alkene respectively in chromatographic column 2, but alcohol ketone impurity composition is because polarity can obtain good separating effect very by force in chromatographic column 2.Adopt mass detector quantitative by characteristic ion, utilize the selectivity feature of mass detector, can get rid of the interference that hydrocarbon component is measured methyl tert-butyl ether, acetaldehyde, propionic aldehyde and butyraldehyde, reduce requirement to chromatographic resolution, therefore adopt olefin product that Gas Chromatography/Mass Spectrometric Method can Accurate Determining complexity as the content of the oxygenatedchemicals except dimethyl ether in MTO product.Complicated alkene sample is after Gas Chromatography/Mass Spectrometric Method is analyzed, extract feature quota ion, can get rid of because separating the interference of the bad hydrocarbon component causing to oxygenatedchemicals, adopt retention time and characteristic ion to carry out quantitative and qualitative analysis, adopt external standard method quantitatively to calculate.Utilize mass spectrum to carry out full scan analysis, can carry out qualitative analysis accurately to the Oxygen-containing Components in complicated alkene sample.If the Oxygen-containing Components content in assorted alkene sample is very low, can also utilize mass spectrum to select ion scan analysis, thereby improve the sensitivity of analyzing, reduce detectability.
Use the method for oxygenatedchemicals in heartcut gas Chromatographic Determination light olefin of the present invention for analyzing the standard model that contains methyl tert-butyl ether, acetaldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, sec-butyl alcohol, 2 pentanone, 3-hexanone, the analytic variance of 5 replicate determinations of standard model is all less than 4.1%, adopt the content of each Oxygen-containing Components in external standard method quantitative test standard specimen II, relative error is between-8.9%～-3.5%, quantitatively accurately and reliably, data precision is good.Analytical approach of the present invention is measured for a kind of oxygenatedchemicals of light olefin product sample, complicated alkene sample is after separating, obtain total ion current figure, the component such as acetaldehyde, propionic aldehyde can not separate completely with some hydrocarbon components, but by extracting behind feature quota ion peak, the component such as acetaldehyde, propionic aldehyde is not disturbed, and illustrates by mass spectrographic selectivity to be that feature quota ion can reduce the requirement to chromatographic resolution, gets rid of because separating the interference of the bad hydrocarbon component causing to oxygenatedchemicals.The analysis data declaration of table 5, analytical approach of the present invention is measured for a kind of oxygenatedchemicals of light olefin product sample, acetaldehyde in can working sample, propionic aldehyde, butyraldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, 3-methyl-2-butanone, propione, 2 pentanone, 3-methyl-2 pentanone, nearly 13 kinds of aldehyde ketone alcohols oxygenatedchemicalss of 3-hexanone, wherein most of component is that some standard methods that in light olefin, oxygenatedchemicals is measured are unmeasured, and the result repeatability of 2 replications is good.Standard specimen and light olefin product actual sample analyze data declaration analytical approach of the present invention adopt characteristic ion quantitatively to the requirement separating reduce, the low-carbon (LC) aldehyde alcohol ketone Oxygen-containing Components of analysis more comprehensively, quantitative advantage accurately, obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of chromatographic analysis device of the present invention;
Fig. 2 is the total ion current figure that standard model provided by the invention is analyzed;
Fig. 3 is the total ion current figure of a kind of light olefin product sample analysis provided by the invention;
Fig. 4 is the feature quota ion peak that light olefin product sample analysis extracts.
Wherein, 1 is chromatogram split sampling mouth, and 2 is TCEP[1,2,3-tri-(2-cyanoethoxyl) propane] capillary chromatographic column, 3 is mass detector (MSD).
1a is methyl tert-butyl ether peak, and 2a is acetaldehyde peak, and 3a is methyl alcohol peak, and 4a is acetone peak, and 5a is isopropyl alcohol peak, and 6a is ethanol peak, and 7a is butanone peak, and 8a is sec-butyl alcohol peak, and 9a is 2 pentanone peak, and 10a is isobutyl alcohol, and 11a is 3-hexanone peak;
1b is acetaldehyde peak, and 2b is propionic aldehyde peak, and 3b is methyl alcohol peak, and 4b is acetone peak, 5b is isopropyl alcohol peak, and 6b is butyraldehyde peak, and 7b is ethanol peak, and 8b is butanone peak, 9b is 3-methyl-2-butanone peak, and 10b is tertiary pentanone peak, and 11b is 2 pentanone peak, and 12b is 3-methyl-2 pentanone peak; 13b is 3-hexanone peak;
1c is acetaldehyde peak, and 2c is propionic aldehyde peak, and 3c is methyl alcohol peak, and 4c is acetone peak, 5c is isopropyl alcohol peak, and 6c is butyraldehyde peak, and 7c is ethanol peak, and 8c is butanone peak, 9c is 3-methyl-2-butanone peak, and 10c is propione peak, and 11c is 2 pentanone peak, and 12c is 3-methyl-2 pentanone peak; 13c is 3-hexanone peak.
Embodiment
Below in conjunction with accompanying drawing, provide preferred embodiment of the present invention, and be described in detail, enable to understand better function, the feature of analytical approach of the present invention.
As shown in Figure 1, chromatographic analysis device of the present invention comprises chromatogram split sampling mouth 1, chromatographic column 2 and mass detector 3.According to the specific works flow process of analytical approach of the present invention be: light olefin gaseous sample adopts six logical gas sampling valve sample introductions, after 1 vaporization of chromatogram split sampling mouth, entering chromatographic column 2 separates, then detected by mass detector 3, extract the feature quota ion peak of oxygenatedchemicals also quantitatively.
Embodiment 1
According to the analytical approach of the invention described above, the standard model I and the II that contain methyl tert-butyl ether, acetaldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, sec-butyl alcohol, 2 pentanone, isobutyl alcohol, 3-hexanone are analyzed, each replication 5 times, extract characteristic ion peak the integration peak area of each component, calculate the relative standard deviation of each component peaks area.Canonical analysis condition is in table 1, and standard specimen I and II join structure and character quota ion in table 2, make solvent with n-pentane, and the total ion current figure of standard specimen II is shown in Fig. 2.Take standard specimen I as outer standard specimen, for treating test sample, calculate content and the relative error of each component in standard specimen II with standard specimen II, measurement and calculation the results are shown in following table 3.
Table 1 canonical analysis condition
Table 2 standard model I and II join structure and character quota ion
The measurement and calculation result of table 3 standard model I and II
The analysis data declaration of table 3, the analytic variance of 5 replicate determinations of standard model is all less than 4.1%, adopts the content of each Oxygen-containing Components in external standard method quantitative test standard specimen II, and relative error is between-8.9%～-3.5%, quantitatively accurately and reliably, data precision is good.
In addition, should be appreciated that, although above-described embodiment 1 has only been enumerated TCEP[1,2,3-tri-(2-cyanoethoxyl)] propane capillary chromatographic column tests, the chromatographic column of other strong polarity also can be used in the method for the invention, and for example fixing is the chromatographic column of polyglycol mutually, the oxygenatedchemicals that it can be used in Analysis of Complex Olefins matrix equally.Certainly,, due to the difference of the concrete component of complicated Olefins matrix, those skilled in the art can select suitable chromatographic column to analyze in conjunction with common practise.In like manner, although the carrier gas flux in above-described embodiment is selected as 1.0mL/min(He), other carrier gas flux is also feasible, is preferably 0.5～3.0mL/min, more preferably 0.8～2.0mL/min, more preferably 0.9～1.5mL/min.
Embodiment 2
According to the analytical approach of the invention described above, a kind of light olefin product actual sample is analyzed, adopt corrected area normalization method quantitative.Spectrometry condition is in table 4, and the total ion current figure of sample analysis is shown in Fig. 3, and the feature quota ion peak figure of extraction is shown in Fig. 4, and the feature quota ion of each Oxygen-containing Components and quantitative analysis results are in table 5.
The typical chromatographiccondition of table 4
Feature quota ion and the quantitative analysis results of the each Oxygen-containing Components of table 5
Fig. 3 can find out, complicated alkene sample is after separating, obtain total ion current figure, the component such as acetaldehyde, propionic aldehyde can not separate completely with some hydrocarbon components, but the feature quota ion peak of the extraction of Fig. 4 can be found out, the component such as acetaldehyde, propionic aldehyde is not disturbed, and illustrates by mass spectrographic selectivity to be that feature quota ion can reduce the requirement to chromatographic resolution, gets rid of because separating the interference of the bad hydrocarbon component causing to oxygenatedchemicals.The analysis data declaration of table 5, analytical approach of the present invention is measured for a kind of oxygenatedchemicals of light olefin product sample, acetaldehyde in can working sample, propionic aldehyde, butyraldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, 3-methyl-2-butanone, propione, 2 pentanone, 3-methyl-2 pentanone, nearly 13 kinds of aldehyde ketone alcohols oxygenatedchemicalss of 3-hexanone, wherein most of component is that some standard methods that in light olefin, oxygenatedchemicals is measured are unmeasured, and the result repeatability of 2 replications is good.
In addition, should be appreciated that, although above-described embodiment 2 has only been enumerated TCEP[1,2,3-tri-(2-cyanoethoxyl)] propane capillary chromatographic column tests, the chromatographic column of other strong polarity also can be used in the method for the invention, and for example fixing is the chromatographic column of polyglycol mutually, the oxygenatedchemicals that it can be used in Analysis of Complex Olefins matrix equally.Certainly,, due to the difference of the concrete component of complicated Olefins matrix, those skilled in the art can select suitable chromatographic column to analyze in conjunction with common practise.In like manner, although the carrier gas flux in above-described embodiment is selected as 1.0mL/min(He), other carrier gas flux is also feasible, is preferably 0.5～3.0mL/min, more preferably 0.8～2.0mL/min, more preferably 0.9～1.5mL/min.
Above-described, be only preferred embodiment of the present invention, not in order to limit scope of the present invention, the above embodiment of the present invention can also make a variety of changes.Be that simple, the equivalence that every claims according to the present patent application and description are done changes and modify, all fall into the claim protection domain of patent of the present invention.The present invention not detailed description be routine techniques content.
Claims (7)
1. the Spectrometry method that in complicated Olefins matrix, oxygenatedchemicals is measured, take the potpourri that contains oxygenatedchemicals and light hydrocarbons as analyzing material, analyze by gas chromatography-mass spectrum device, it is characterized in that, described analysis material is by chromatogram split sampling mouth (1) sample introduction, chromatographic column (2) by strong polarity separates, and is then detected and is undertaken quantitatively by characteristic ion by mass detector (3).
2. the Spectrometry method that in complicated Olefins matrix according to claim 1, oxygenatedchemicals is measured, it is characterized in that, described chromatographic column (2) is TCEP[1,2,3-tri-(2-cyanoethoxyl)] propane capillary chromatographic column or polyglycol be the capillary chromatographic column of fixing phase.
3. the Spectrometry method that in complicated Olefins matrix according to claim 1, oxygenatedchemicals is measured, is characterized in that, described chromatographic column (2) is take helium as carrier gas, and carrier gas flux is 0.5～3.0 ml/min, and chromatogram column temperature is 40～130 ℃.
4. the Spectrometry method that in complicated Olefins matrix according to claim 1, oxygenatedchemicals is measured, it is characterized in that, described oxygenatedchemicals is selected from: methyl tert-butyl ether, acetaldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, sec-butyl alcohol, 2 pentanone, 3-hexanone.
5. the Spectrometry method that in complicated Olefins matrix according to claim 1, oxygenatedchemicals is measured, it is characterized in that, described oxygenatedchemicals is selected from: acetaldehyde, propionic aldehyde, butyraldehyde, methyl alcohol, acetone, isopropyl alcohol, ethanol, butanone, 3-methyl-2-butanone, propione, 2 pentanone, 3-methyl-2 pentanone and 3-hexanone.
6. the Spectrometry method that in complicated Olefins matrix according to claim 1, oxygenatedchemicals is measured, is characterized in that, described oxygenatedchemicals does not comprise dimethyl ether.
7. the Spectrometry method that in complicated Olefins matrix according to claim 1, oxygenatedchemicals is measured, is characterized in that, described analysis material is the reaction product of methanol-to-olefins.
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| CN109374804A (en) * | 2018-10-31 | 2019-02-22 | 内蒙古中煤蒙大新能源化工有限公司 | The chromatogram analysis method of bromopropane product in a kind of production of MTO technology |
| CN110286164A (en) * | 2019-05-06 | 2019-09-27 | 北京水木滨华科技有限公司 | A kind of qualitative and quantitative detecting method and detection device of liquid material |
| CN110568085A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Method for determining acetonitrile content in sample |
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- 2012-10-31 CN CN201210429247.6A patent/CN103792297A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110568085A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Method for determining acetonitrile content in sample |
| 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 |
| CN109374804A (en) * | 2018-10-31 | 2019-02-22 | 内蒙古中煤蒙大新能源化工有限公司 | The chromatogram analysis method of bromopropane product in a kind of production of MTO technology |
| CN109374804B (en) * | 2018-10-31 | 2020-11-03 | 内蒙古中煤蒙大新能源化工有限公司 | Chromatographic analysis method for propane product in methanol-to-olefin process production |
| CN110286164A (en) * | 2019-05-06 | 2019-09-27 | 北京水木滨华科技有限公司 | A kind of qualitative and quantitative detecting method and detection device of liquid material |
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Application publication date: 20140514 |