CN102565248A - Chromatographic column, preparation method thereof and application thereof to analysis of mixture comprising 1,2-dichloroethane, ethyl chloride, methyl chloride and/or vinyl chloride - Google Patents
Chromatographic column, preparation method thereof and application thereof to analysis of mixture comprising 1,2-dichloroethane, ethyl chloride, methyl chloride and/or vinyl chloride Download PDFInfo
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- CN102565248A CN102565248A CN2010106149897A CN201010614989A CN102565248A CN 102565248 A CN102565248 A CN 102565248A CN 2010106149897 A CN2010106149897 A CN 2010106149897A CN 201010614989 A CN201010614989 A CN 201010614989A CN 102565248 A CN102565248 A CN 102565248A
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Abstract
The invention relates to a chromatographic column for performing gas chromatographic analysis on a mixture comprising 1,2-dichloroethane, ethyl chloride, methyl chloride and/or vinyl chloride. A fixed phase is a mixture of GDX 502 of 60-80 meshes and Porapak P of 80-100 meshes, wherein the weight ratio of GDX 502 to Porapak P is (0.3-0.6):1. The invention further relates to a method for preparing the chromatographic column, which comprises the following step of: preparing a mixture of GDX 502 of 60-80 meshes and Porapak P of 80-100 meshes for serving as the fixed phase. The invention further relates to a method for performing gas chromatographic analysis on the mixture comprising 1,2-dichloroethane, ethyl chloride, methyl chloride and/or vinyl chloride, which comprises the following step of: making the mixture pass through the chromatographic column. The GDX 502 with a good separating effect on methyl chloride and Porapak P with good separating effects on ethyl chloride and vinyl chloride are combined together, and the mixture is taken as the fixed phase, so that 1,2-dichloroethane, ethyl chloride, methyl chloride and/or vinyl chloride in the mixture can be separated effectively and quantified accurately.
Description
Technical field
The present invention relates to be used for to comprising 1; The potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the chromatographic column of gas chromatographic analysis; Further; Relate to the method for preparing said chromatographic column and said chromatographic column to comprising 1, the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the application in the gas chromatographic analysis.
Background technology
Under the silver catalyst effect, making ethene and oxygen reaction produce oxirane is an important industrial flow.Need in unstripped gas, add trace 1,2-ethylene dichloride or ethyl chloride are as suppressant.In the unstripped gas 1,2-ethylene dichloride or ethyl chloride partial reaction through the silver catalyst bed time generates chloromethanes, ethyl chloride and vinyl chloride, and is recycled in the unstripped gas with unreacted ethene and oxygen.Need accurately to analyze in the unstripped gas 1 in industrial processes control, estimating, the concentration of 2-ethylene dichloride, ethyl chloride, chloromethanes and vinyl chloride with silver catalyst.
At present; In the ethylene oxide/ethylene glycol industrial installation, mainly adopt following two kinds of methods that above-mentioned chloride is analyzed: vapor-phase chromatography, wherein use packed column or capillary column; And with hydrogen as carrier gas; But said method only analyzes 1, and the concentration of 2-ethylene dichloride or ethyl chloride is not analyzed other chloride; Use the total concentration of enclosed pasture appearance analyzing chloride, but said method can not be measured various muriatic concentration respectively, and accuracy of analysis is not high.
For example, " micro-ethylene dichloride in the gas chromatography determination oxirane circular response gas "; Sun Ying; The Guangxi chemical industry, calendar year 2001, the 30th volume, the 1st phase, the 27-29 page or leaf has been reported with β, and β '-oxydipropionitrile is that stationary phase is with trace 1 in the gas chromatography determination oxirane circular response gas, 2-ethylene dichloride content.
For example, " trace 1 in the gas chromatography determination ethylene oxide reactor gas, 2-ethylene dichloride "; Zheng Lihong, summer satellite, Jiang Jian, Wang Xin, coroner's spring fine jade; Analytical instrument, 2007, the 2nd phase, the 38-40 page or leaf was reported to use to contain with silicone oil II immobile liquid and has been coated with trace 1 in the chromatographic column adopting gas chromatography determination ethylene oxide reactor of Chromosorb WHP carrier of stain, 2-ethylene dichloride content.
Newly-built ethylene oxide/ethylene glycol industrial installation needs accurately to analyze all muriatic concentration.The corresponding analysis method mainly adopts the online two-dimensional gas chromatography appearance of Siemens, and uses two packed columns and various fixed phase and immobile liquid.Said method is complicated, apparatus expensive, and pre-service is had relatively high expectations to appearance gas.
Summary of the invention
In view of above-mentioned prior art situation; The present inventor is to comprising 1; The potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the technical field of gas chromatographic analysis and has carried out research extensively and profoundly; In the hope of can to wherein 1,2-ethylene dichloride, chloromethanes, ethyl chloride and/or vinyl chloride effectively separate and accurately quantitatively.The result finds can be through using the chromatographic column realization above-mentioned purpose of stationary phase as the potpourri of 60-80 purpose GDX502 and 80-100 purpose Porapak P.The inventor just is being based on above-mentioned discovery and is accomplishing the present invention.
The purpose of this invention is to provide a kind of being used for comprising 1, the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the chromatographic column of gas chromatographic analysis.
Another object of the present invention provides a kind of method for preparing above-mentioned chromatographic column.
A purpose more of the present invention provides a kind of to comprising 1, and the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the method for gas chromatographic analysis.
One aspect of the present invention provides a kind of and has been used for comprising 1; The potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the chromatographic column of gas chromatographic analysis; The stationary phase of said chromatographic column is the potpourri of 60-80 purpose GDX 502 and 80-100 purpose Porapak P; Wherein GDX 502 is 0.3-0.6 with the weight ratio of Porapak P: 1, and preferred 0.4-0.5: 1.
The present invention provides a kind of method for preparing above-mentioned chromatographic column on the other hand; Said method comprises that the potpourri with 60-80 purpose GDX 502 and 80-100 purpose Porapak P is used as stationary phase; Wherein GDX 502 is 0.3-0.6 with the weight ratio of Porapak P: 1, and preferred 0.4-0.5: 1.
Further aspect of the present invention provides that a kind of the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the method for gas chromatographic analysis to comprising 1, and said method comprises makes said potpourri through above-mentioned chromatographic column.
The present invention will have the GDX 502 of well separated effect to chloromethanes and combine with the Porapak P that ethyl chloride and vinyl chloride is had the well separated effect and it is used as stationary phase; Got rid of the interference of high concentration materials such as methane, ethene, acetylene, propylene and oxirane effectively; Guaranteed trace 1, effective separation of 2-ethylene dichloride, chloromethanes, ethyl chloride and/or vinyl chloride and accurately quantitative.
Of the present invention these with other purpose, feature and advantage after integral body is considered the present invention, will be easy to understood by those of ordinary skill.
Description of drawings
Fig. 1 is for to analyze the gas chromatogram that is obtained according to chloromethanes, ethyl chloride and vinyl chloride in 1 pair of potpourri of embodiment.
Fig. 2 is that the 2-ethylene dichloride is analyzed the gas chromatogram that is obtained according to 1 in 2 pairs of potpourris of embodiment.
Embodiment
In commercial production, can under the silver catalyst effect, utilize oxygen that oxidation of ethylene is prepared oxirane, it for example specifically describes in Kirk-othmer; Ency.of chem.Techn.; 1965, the 8 volumes in the 523-558 page or leaf, are attached to related content among this paper at this by reference.Equally; Ethene capable of using and oxygen generate respective performances such as the catalytic activity or the stability etc. to silver catalyst that are reflected in the silver catalyst evaluating apparatus of oxirane and estimate; It for example specifically describes in japanese kokai publication hei 2-104579, by reference related content is attached among this paper at this.
The flow of feed gas that will have following composition usually infeeds through in the industrial installation or silver catalyst evaluating apparatus that oxidation of ethylene are prepared oxirane:
Ethene 20-40 mole %;
Oxygen 5-9 mole %;
Carbon dioxide 0.1-15 mole %;
Ethane 0-2 mole %;
Cause steady gas 0-60 mole %;
Oxirane 0-0.5 mole %;
Wherein usually with nitrogen or methane as causing steady gas.
Ethene in the flow of feed gas, oxygen and cause steady gas and also can following gaseous impurities be brought in the reaction system usually:
Propane≤50 molar ppm;
Hydrogen≤20 molar ppm;
Acetylene≤80 molar ppm;
Carbon monoxide≤20 molar ppm;
C
7Above hydrocarbon≤20 molar ppm.
Simultaneously, also in said device, add 1 of 0.1-10 molar ppm, 2-ethylene dichloride or ethyl chloride are as suppressant.
In ethene and oxygen reaction generation oxirane (EO), the suppressant in the flow of feed gas can generate other chloride through the silver catalyst bed time.With 1,2-ethylene dichloride (EDC) is as under the situation of suppressant, 1, the 2-ethylene dichloride in said apparatus further reaction generate ethyl chloride (EC), chloromethanes (MC) and vinyl chloride (VC).Ethyl chloride is being used as under the situation of suppressant, and ethyl chloride further reacts in said apparatus and generates chloromethanes and vinyl chloride.
From said apparatus, product gas flow is taken out, and required product oxirane is separated.For improving the conversion ratio of raw material, especially ethene, need unreacted ethene and oxygen be recycled in the said apparatus.
In industrial processes control and silver catalyst are estimated, need accurately to analyze in the recirculated air 1, the concentration of 2-ethylene dichloride, chloromethanes, ethyl chloride and vinyl chloride.
For this reason; One aspect of the present invention provides a kind of and has been used for comprising 1; The potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the chromatographic column of gas chromatographic analysis; The stationary phase of said chromatographic column is the potpourri of 60-80 purpose GDX 502 and 80-100 purpose Porapak P, and wherein the weight ratio of GDX502 and Porapak P is 0.3-0.6: 1.In said chromatographic column, GDX 502 is preferably 0.4-0.5 with the weight ratio of Porapak P: 1.
GDX 502 (GDX502 or GDX-502) is a styrene diethylene benzene copoly mer, and it is commercially available, for example from Tianjin chemical reagent two factories.502 pairs of chloromethanes of GDX have good separating effect.Porapak P is styrene-ethyl styrene-divinyl benzene copolymer, available from U.S. Waters company.Porapak P has good separating effect to ethyl chloride and vinyl chloride.
The internal diameter of said chromatographic column is 1.5-6mm, and length is 1-4m, and can for example be stainless steel column, glass column or quartz column.
For this reason, the present invention also provides a kind of method for preparing above-mentioned chromatographic column, and said method comprises that the potpourri with 60-80 purpose GDX 502 and 80-100 purpose Porapak P is used as stationary phase, and wherein GDX 502 is 0.3-0.6 with the weight ratio of Porapak P: 1.GDX 502 is preferably 0.4-0.5 with the weight ratio of Porapak P: 1.
Internal diameter and length according to chromatographic column to be filled; A certain amount of GDX 502 and Porapak P are mixed by above-mentioned weight ratio, and for example filling it into internal diameter for example with the mode that vacuumizes then is that 1.5-6mm and length are can obtain chromatographic column of the present invention in stainless steel column, glass column or the quartz column of 1-4m.
The present invention provides also that a kind of the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the method for gas chromatographic analysis to comprising 1, and said method comprises makes said potpourri through chromatographic column of the present invention.
Make said potpourri through chromatographic column of the present invention before, chromatographic column is aging.Particularly, be described below and wear out: at stationary phase filling access end the chromatographic column for preparing is connected with the chromatograph injection port, it is open that the other end then keeps; With 30mL/ minute flow logical nitrogen 10-120 minute to chromatographic column, then with 10 ℃ of/minute temperature programmes to 200-240 ℃, continued logical nitrogen 24-56 hour, stop logical nitrogen at last and be cooled to room temperature.
Saidly comprise 1, the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride is for mainly preparing the industrial installation of oxirane or the recirculated air of silver catalyst evaluating apparatus by passing through of forming of ethene and oxygen with oxidation of ethylene.With 1, the 2-ethylene dichloride is as under the situation of suppressant, and recirculated air comprises ethene, oxygen, 1,2-ethylene dichloride, ethyl chloride, chloromethanes and vinyl chloride.Ethyl chloride is being used as under the situation of suppressant, and recirculated air comprises ethene, oxygen, ethyl chloride, chloromethanes and vinyl chloride.
In above-mentioned recirculated air, 1,2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride are traces, promptly its concentration is respectively at 0.01 mole below the %.
Can be according to the present invention the internal diameter and the length of chromatographic column select suitable carrier gas flux and sample size.In the methods of the invention, use 20-35mL/ minute N
2As carrier gas, sample size for example is 0.5-2.0mL.
One skilled in the art will appreciate that the inventive method is applicable to that also the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out gas chromatographic analysis to wherein comprising high concentration 1 after suitably adjusting.
Those skilled in the art it is to be further understood that; Comprise 1 except that above-mentioned; Outside the recirculated air of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride, the inventive method also is applicable to and comprises 1, other gaseous mixture of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride; Perhaps comprise 1, the liquid mixture of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride.
Chromatographic column of the present invention will have the GDX 502 of well separated effect to chloromethanes and be used as stationary phase with the Porapak P that ethyl chloride and vinyl chloride is had the well separated effect; Got rid of the interference of high concentration materials such as methane, ethene, acetylene, propylene and oxirane effectively; Guaranteed trace 1, effective separation of 2-ethylene dichloride, chloromethanes, ethyl chloride and/or vinyl chloride and accurately quantitative; The method that the present invention carries out gas chromatographic analysis correspondingly can realize in the potpourri 1, effective separation of 2-ethylene dichloride, chloromethanes, ethyl chloride and/or vinyl chloride and accurately quantitatively, and need not sample is carried out any special pre-treatment.
Embodiment
Hereinafter specifically describes the present invention through the reference implementation example, but said embodiment does not constitute any restriction to the scope of the invention.
Used gas chromatograph is the Agilent 7890A type gas chromatograph from U.S. Agilent company.
Embodiment 1
The flow of feed gas that will have following composition is with 4500h
-1Air speed infeed in the oxirane industrial installation, said device is equipped with the bed of 26 tons of YS-7 type silver catalysts (catalyzer Beijing Yanshan Mountain branch office of China Petrochemical Industry):
28.5 moles of % of ethene;
7.90 moles of % of oxygen;
6.50 moles of % of carbon dioxide;
0.35 mole of % of ethane;
46.2 moles of % of methane;
2.50 moles of % of oxirane.
Simultaneously, also the flow with 385 Grams Per Hours adds ethyl chloride as suppressant to flow of feed gas, under the pressure of 225 ℃ temperature and 2.1Mpa, makes ethene and oxygen reaction generate oxirane.From said device, product gas flow is taken out, and required product oxirane is separated.The gaseous mixture that mainly comprises unreacting ethylene and oxygen is recycled in the said device.The chloride that at this moment, need carry out gas chromatographic analysis in the recirculated air is chloromethanes, ethyl chloride and vinyl chloride.
Used chromatographic column is the stainless steel column of Φ 3mm * 2m, and wherein the potpourri with 2.5g GDX 502 (Tianjin chemical reagent two factories) and 5g Porapak P (U.S. Waters company) is used as stationary phase.
On chromatographic work station, set up following analytical approach 1:
Injector temperature: 120 ℃;
Carrier gas: 22mL N
2/ minute;
Column temperature: 75 ℃ (2 minutes), then with 8 ℃ of/minute temperature programmes to 105 ℃;
Fid detector: 200 ℃, 35mL hydrogen/minute, the 300mL air/minute, 10mL nitrogen/minute;
Sample size: 1mL.
The chloromethanes, ethyl chloride and the vinyl chloride that call in 1 pair of said recirculated air of analytical approach are analyzed, and the gained result sees Fig. 1.
As shown in Figure 1, the appearance time of chloromethanes, vinyl chloride and ethyl chloride was followed successively by 6.81 minutes, 8.68 minutes and 12.26 minutes, and its concentration is respectively 1.52 molar ppm, 2.10 molar ppm and 3.32 molar ppm.
Embodiment 2
The flow of feed gas that will have following composition is with 5000h
-1Air speed infeed in the oxirane industrial installation, said device is equipped with the bed of 24 tons of YS-7 type silver catalysts (catalyzer Beijing Yanshan Mountain branch office of China Petrochemical Industry):
29.1 moles of % of ethene;
8.10 moles of % of oxygen;
5.50 moles of % of carbon dioxide;
0.25 mole of % of ethane;
48.8 moles of % of methane;
2.35 moles of % of oxirane.
Simultaneously, also the flow with 150 Grams Per Hours adds 1 to flow of feed gas, and the 2-ethylene dichloride makes ethene and oxygen reaction generate oxirane under the pressure of 238 ℃ temperature and 2.1Mpa as suppressant.From said device, product gas flow is taken out, and required product oxirane is separated.The gaseous mixture that mainly comprises unreacting ethylene and oxygen is recycled in the said device.At this moment, the chloride that need carry out gas chromatographic analysis in the recirculated air is 1,2-ethylene dichloride, chloromethanes, ethyl chloride and vinyl chloride.
Used chromatographic column is the stainless steel column of Φ 3mm * 3m, and wherein the potpourri with 2g GDX 502 (Tianjin chemical reagent two factories) and 5g Porapak P (U.S. Waters company) is used as stationary phase.
On chromatographic work station, set up following analytical approach 2:
Injector temperature: 120 ℃;
Carrier gas: 28mL N
2/ minute;
Column temperature: 165 ℃ (5 minutes);
Fid detector: 200 ℃, 35mL hydrogen/minute, the 350mL air/minute, 8mL nitrogen/minute;
Sample size: 2mL.
The chloromethanes, ethyl chloride and the vinyl chloride that call in 1 pair of said recirculated air of analytical approach are analyzed.
The appearance time of chloromethanes, vinyl chloride and ethyl chloride was followed successively by 6.12 minutes, 7.99 minutes and 11.30 minutes, and its concentration is respectively 0.90 molar ppm, 1.15 molar ppm and 0.132 molar ppm.
Call 1 in 2 pairs of said recirculated airs of analytical approach, the 2-ethylene dichloride is analyzed, and the gained result sees Fig. 2.
As shown in Figure 2,1, the appearance time of 2-ethylene dichloride is 3.51 minutes, its concentration is 0.18 molar ppm.
Claims (10)
1. one kind is used for comprising 1; The potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the chromatographic column of gas chromatographic analysis; The stationary phase of said chromatographic column is the potpourri of 60-80 purpose GDX502 and 80-100 purpose Porapak P; Wherein GDX 502 is 0.3-0.6 with the weight ratio of Porapak P: 1, and preferred 0.4-0.5: 1.
2. the chromatographic column of claim 1, said chromatographic column is that internal diameter is that 1.5-6mm and length are stainless steel column, glass column or the quartz column of 1-4m.
3. method for preparing the chromatographic column of claim 1 or 2; Said method comprises that the potpourri with 60-80 purpose GDX 502 and 80-100 purpose Porapak P is used as stationary phase; Wherein the weight ratio of GDX502 and Porapak P is 0.3-0.6: 1, and preferred 0.4-0.5: 1.
4. one kind to comprising 1, and the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride carries out the method for gas chromatographic analysis, and said method comprises makes the chromatographic column of said potpourri through claim 1 or 2.
5. the method for claim 4, said method also are included in and make said potpourri through before the said chromatographic column that chromatographic column is aging.
6. claim 4 or 5 method; Wherein comprise 1, the potpourri of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride is for mainly preparing the industrial installation of oxirane or the recirculated air of silver catalyst evaluating apparatus by passing through of forming of ethene and oxygen with oxidation of ethylene.
7. the method for claim 6, wherein in said industrial installation or silver catalyst evaluating apparatus with 1, the 2-ethylene dichloride is as suppressant, said recirculated air comprises ethene, oxygen, 1,2-ethylene dichloride, ethyl chloride, chloromethanes and vinyl chloride.
8. the method for claim 6 wherein is used as suppressant with ethyl chloride in said industrial installation or silver catalyst evaluating apparatus, and said recirculated air comprises ethene, oxygen, ethyl chloride, chloromethanes and vinyl chloride.
9. each method among the claim 4-8, wherein 1, the concentration of 2-ethylene dichloride, ethyl chloride, chloromethanes and/or vinyl chloride is respectively at 0.01 mole below the %.
10. each method among the claim 4-9, said method use 20-35mL/ minute N2 as carrier gas, and sample size is 0.5-2mL.
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| CN104001487A (en) * | 2014-06-12 | 2014-08-27 | 雷晓强 | Preparation method of hollow capillary tubular gas chromatographic column in GDX porous polymer series |
| CN104165935A (en) * | 2014-05-30 | 2014-11-26 | 中国海洋石油总公司 | Analyzing and monitoring method for circulating mother liquor during production of 1,2-dichloroethane |
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| CN105929097A (en) * | 2016-06-25 | 2016-09-07 | 江苏正大清江制药有限公司 | Method for measuring chloromethane and chloroethane in dexmedetomidine hydrochloride |
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| CN104165935B (en) * | 2014-05-30 | 2015-11-25 | 中国海洋石油总公司 | The analyzing monitoring method of 1,2-ethylene dichloride production cycle mother liquor |
| CN104001487A (en) * | 2014-06-12 | 2014-08-27 | 雷晓强 | Preparation method of hollow capillary tubular gas chromatographic column in GDX porous polymer series |
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