CN102262130B - Chromatographic method for analyzing content of trace benzene in vinyl benzene products or other hydrocarbon solvents based on flow switch - Google Patents
Chromatographic method for analyzing content of trace benzene in vinyl benzene products or other hydrocarbon solvents based on flow switch Download PDFInfo
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- CN102262130B CN102262130B CN201010183021.3A CN201010183021A CN102262130B CN 102262130 B CN102262130 B CN 102262130B CN 201010183021 A CN201010183021 A CN 201010183021A CN 102262130 B CN102262130 B CN 102262130B
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Abstract
The invention relates to a chromatographic method for analyzing the content of trace benzene in vinyl benzene products or other hydrocarbon solvents based on flow switch, which mainly solves the problems of great difficulty in the establishment of a method and large dead volume of a valve switch system owing to the adoption of the conventional valve switch technology for analyzing the trace benzene in the vinyl benzene products or the other hydrocarbon solvents in the existing chromatographic analysis technology. The problem is perfectly solved by a technical scheme comprising the following steps that: a sample of the vinyl benzene products or the other hydrocarbon solvents is pre-separated by a chromatographic column (5), benzene is cut to a chromatographic column (11) by a flow switch center cutting system (13) to be further separated, and then, the cut benzene is detected by a hydrogen flame ionization detector (10) and quantified through an external standard method, and other components flowing out of the chromatographic column (5) enter into the hydrogen flame ionization detector (10) via a damping column (2) for being detected. The method can be used in industrial production of chromatographic analysis on the content of the trace benzene in the vinyl benzene products or the other hydrocarbon solvents.
Description
Technical field
The present invention relates to a kind of flow switch and analyze the gas chromatography of micro-benzene in styrene product or other varsol.
Background technology
Styrene (SM) is a kind of important basic organic chemical industry raw material, mainly for the production of polystyrene resin (PS), acrylonitrile-butadiene-styrene (ABS) (ABS) resin, styrene-acrylonitrile copolymer (SAN) resin, styrene-butadiene rubber (SBR), ion exchange resin, unsaturated polyester (UP) and styrene series thermoplastic elastomer (as SBS) etc.In addition, also can be used for the industries such as pharmacy, dyestuff, agricultural chemicals and ore dressing, purposes is very extensive.Current cinnamic main production is to generate ethylbenzene by benzene-alkylation, then dehydrogenation generates styrene.China's styrene industry development is rapid, and newly-built reorganization and expansion device is gone into operation, and output and technical merit comparatively fast improve.Benzene is a kind of strong carcinogen, the diseases such as energy leukemogenesis and alpastic anemia, when the styrene that contains micro-benzene is during for the production of the polystyrene material (cutlery box) of food-grade, micro-benzene can enter human body by food, can produce harm to health.Benzene in other varsol also can see through various approach and be penetrated into environment and human body, thereby in styrene product or other varsol, the mensuration of micro-benzene has great significance to environmental protection and health of human body.
In U.S. ASTM D2827-04 " styrene product standard " standard, clearly stipulated that in styrene, benzene content can not surpass 1mg/kg, in corresponding method of testing standard A STM D6229-06 " standard method of test of the micro-benzene in capillary gas chromatography varsol ", adopt double-column series valve blowback system, effective micro-benzene in separating phenylethylene, lowest detectable limit reaches 1mL/m
3(massfraction needs to proofread and correct).
In ASTM D6229-06 " standard method of test of the micro-benzene in capillary gas chromatography varsol " standard method, adopt traditional valve handoff technique, it is larger that method is set up difficulty, and valve switched system dead volume is larger.In the current styrene product of China, do not control benzene content, there is no to analyze accordingly the standard method of micro-benzene in styrene product yet.
In standard GB/T/T 12688.1-1998 " the mensuration capillary gas chromatography of industrial styrene purity " standard method, adopting polyglycol polar column is that analytical column is analyzed cinnamic purity and impurity, because benzene and some non-aromatic component can not be completely separated, thereby can not be for measuring the micro-benzene content of styrene product.Benzene in other varsol does not have easily extensively applicable chromatogram analysis method yet.
Summary of the invention
Technical matters to be solved by this invention is while exist analyzing in styrene or other varsol micro-benzene in existing chromatographic technique, adopt traditional valve handoff technique, it is larger that method is set up difficulty, the problem that valve switched system dead volume is larger, provides a kind of new flow switch to analyze the chromatographic process of micro-benzene in styrene product or other varsol.The method has advantages of that method foundation and processing ease, employing capillary chromatographic column, zero dead volume, cut coverage are narrow, quantitatively accurately and extensively applicable.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: flow switch is analyzed the chromatographic process of micro-benzene content in styrene product or other varsol, take styrene product or other varsol as analyzing material, by flow switch heartcut chromatogram arrangement, analyze, styrene or other varsol sample are by chromatogram split sampling mouth 4 sample introductions, by chromatographic column 5, carry out pre-separation, benzene is cut to chromatographic column 11 by flow switch heartcut system 13, further separated, then by flame ionization ditector 10, detected and adopt external standard method quantitative, all the other components that flow out in chromatographic column 5 enter flame ionization ditector 1 by damping column 2 and detect, wherein chromatographic column 5 is methyl silicone capillary chromatographic column, chromatographic column 11 is FFAP capillary chromatographic column, damping column 2 is the quartz capillary void column that resistance is identical with chromatographic column 11.
In technique scheme, the carrier gas of chromatographic column 5 (nitrogen) flow is 2.5～5.0mL/min, and temperature is 40～60 ℃; The carrier gas of chromatographic column 11 (nitrogen) flow is 4.0～8.0mL/min, and temperature is 40～60 ℃; Carrier gas flux in chromatographic column 11 (nitrogen) is higher more than 50% than the carrier gas flux in chromatographic column 5 (nitrogen), to guarantee that cutting completely; Carrier gas (nitrogen) flow of damping column 2 and chromatographic column 11 is identical.
Nonpolar chromatographic column 5 can be carried out initial gross separation by boiling point by the component in styrene or other varsol, a small amount of C that benzene and boiling point are close
7non-aromatics flows out jointly.Piece-rate system adopts the pressure of split sampling mouth 4 and the pressure of aux. pressure controller 9 to carry out the adjusting of gas flow; By electromagnetic switching valve 8, three flow switch heartcut systems 13 that form without threeway 3,6,12 and the damper tube 7 of dead volume, carry out carrier gas and flow to and switch, Figure 1A and Figure 1B show that respectively carrier gas when electromagnetic switching valve 8 is closed and opened flows to; Damping column 2 and chromatographic column 11 are carried out pressure equilibrium adjusting.Flow switch heartcut system 13, can accurately be cut to strong polarity chromatographic column 11 by component benzene completely not separated in chromatographic column 5 further separated, and chromatographic column 11 can be completely separated with non-aromatic component by benzene completely not separated in chromatographic column 5.The resistance of damping column 2 and chromatographic column 11 equate and carrier gas flux identical, the carrier gas flux in chromatographic column 11 (nitrogen) is higher more than 50% than the carrier gas flux in chromatographic column 5 (nitrogen), to guarantee that cutting is completely.In sample analysis, adopt very little split ratio (5: 1) to improve detection sensitivity, to reduce detectability, and adopt external standard method or solvent external standard method quantitative, to guarantee to analyze accuracy and the precision of data.Flow diced system has advantages of that cut coverage is narrow, precision is high, thereby the method is widely used in the mensuration of micro-benzene in various varsols.
Use the gas chromatography of micro-benzene in flow switch analysis styrene product of the present invention or other varsol for analyzing cinnamic standard model, the calibration curve correlation coefficient r of its benzene
2be 0.9996, the relative error that standard specimen is measured is between-0.68%～6.4%, and styrene actual sample quantitative analysis results is consistent with ASTM D6229-06 standard method measurement result.Quantitative analytical data explanation, the inventive method foundation and processing ease, quantitatively accurate, data precision is good, has 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 chromatogram that styrene actual sample provided by the invention is analyzed.
In Fig. 1,1 is flame ionization ditector FID2B, 2 is damping column, 3,6 and 12 is zero dead volume T-valve, and 4 is chromatogram split sampling mouth, and 5 for containing methyl silicone capillary chromatographic column, 7 is flow switch damper tube, 8 is electromagnetic switching valve, and 9 is aux. pressure controller, and 10 is flame ionization ditector FID1A, 11 is FFAP capillary chromatographic column, and 13 is flow switch heartcut system.Figure 1A is the process flow diagram of electromagnetic switching valve 8 while closing, and Figure 1B is the process flow diagram of electromagnetic switching valve 8 while opening.
In Fig. 2, upper Fig. 1 is benzene, and 2 is non-aromatics, and figure below is the chromatographic peak of all the other components in styrene.
Workflow in Fig. 1 is: styrene sample or other varsol adopt liquid automatic sampler sample introduction, enters chromatographic column 5 and carry out initial gross separation after 4 vaporizations of chromatogram split sampling mouth.While being about to flow out from chromatographic column 5 at benzene peak, switch electromagnetic switching valve 8, the gas circuit of change system flows to, benzene completely not separated in chromatographic column 5 and non-aromatic component are cut to chromatographic column 11 further separated, at benzene peak completely from chromatographic column 5 flows out, switching solenoid valve, makes all the other components flow out from damping column 2 again.The benzene flowing out from chromatographic column 11 is completely separated is detected by flame ionization ditector 10, and adopts external standard method quantitative.After benzene flows out completely, reduce the pressure of split sampling mouth 4, improve the pressure of aux. pressure controller 9, by the heavy constituent blowback of not flowing out in chromatographic column 5, from the shunting outlet of split sampling mouth 4, flow out, to guarantee the not analysis of interfere with subsequent sample, after blowback in to be reorganized minute, analyze and finish.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Press the flow process of Fig. 1, the standard model of benzene is analyzed, typical chromatographiccondition is in Table 1.Wherein, with standard specimen 1
#～4
#draw calibration curve, then with standard specimen 2
#with 4
#as testing sample, analyze 5 times, by calibration curve, benzene is quantitatively calculated.Standard specimen composition and analysis result are in Table 2.
The typical chromatographiccondition of table 1
Table 2 standard model analysis result
The analysis data declaration of table 2, the correlation coefficient r of benzene calibration curve
2be 0.9996, linear relationship is good, and the relative error that standard specimen is measured is between-0.68%～6.4%, quantitatively accurate.
[embodiment 2]
Press the flow process of Fig. 1, styrene actual sample A and B are analyzed, and compare with ASTM D6229-06 standard method measurement result.Typical color spectral condition is in Table 3, and quantitative analysis results is in Table 4.The explanation of table 4 quantitative analysis results, two kinds of methods analyst results are consistent.
The typical chromatographiccondition of table 3
The actual styrene sample analysis of table 4 result
Claims (1)
1. flow switch is analyzed the chromatographic process of micro-benzene content in styrene product or other varsol, take styrene product or other varsol as analyzing material, by flow switch heartcut chromatogram arrangement, analyze, styrene or other varsol sample are by chromatogram split sampling mouth (4) sample introduction, by the first chromatographic column (5), carry out pre-separation, benzene is cut to the second chromatographic column (11) by flow switch heartcut system (13), further separated, then by the second flame ionization ditector (10), detect and adopt external standard method quantitative, all the other enter the first flame ionization ditector (1) in the upper component flowing out of the first chromatographic column (5) by damping column (2) and detect, wherein the first chromatographic column (5) is methyl silicone capillary chromatographic column, the second chromatographic column (11) is FFAP capillary chromatographic column, damping column (2) is the quartz capillary void column that resistance is identical with the second chromatographic column (11),
The nitrogen carrier gas flow of the first chromatographic column (5) is 2.5～5.0mL/min, and temperature is 40～60 ℃; The nitrogen carrier gas flow of the second chromatographic column (11) is 4.0～8.0mL/min, and temperature is 40～60 ℃; Nitrogen carrier gas flow in nitrogen carrier gas throughput ratio the first chromatographic column (5) in the second chromatographic column (11) is high more than 50%, to guarantee that cutting completely; Damping column (2) is identical with the nitrogen carrier gas flow of the second chromatographic column (11); After benzene flows out from the second chromatographic column (11), the nebulizer gas pressure of rising aux. pressure controller (9), the pressure of reduction chromatogram split sampling mouth (4), blowback heavy constituent;
While being about to flow out from the first chromatographic column (5) at benzene peak, switch electromagnetic switching valve (8), the gas circuit of change system flows to, benzene completely not separated in the first chromatographic column (5) and non-aromatic component are cut to the second chromatographic column (11) further separated, at benzene peak completely from the first chromatographic column (5) flows out, switching solenoid valve, makes all the other components flow out from damping column (2) again; The benzene flowing out from the second chromatographic column (11) is completely separated is detected by the second flame ionization ditector (10), and adopts external standard method quantitative; After benzene flows out completely, reduce the pressure of split sampling mouth (4), improve the pressure of aux. pressure controller (9), by the heavy constituent blowback of not flowing out in the first chromatographic column (5), from the shunting outlet of split sampling mouth (4), flow out, to guarantee the not analysis of interfere with subsequent sample, after blowback in to be reorganized minute, analyze and finish.
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| 李继文 等.采用二维气相色谱及毛细管色谱柱分析汽油中苯和甲苯的含量.《色谱》.2009,第27卷(第3期),346-350. |
| 采用二维气相色谱及毛细管色谱柱分析汽油中苯和甲苯的含量;李继文 等;《色谱》;20090531;第27卷(第3期);第347页1.1节至348页2.1节 * |
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