CN100434916C - Industrial flow for analyzing 4-carbon olefin and dedicated instrument for same - Google Patents

Industrial flow for analyzing 4-carbon olefin and dedicated instrument for same Download PDF

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CN100434916C
CN100434916C CNB2005100471462A CN200510047146A CN100434916C CN 100434916 C CN100434916 C CN 100434916C CN B2005100471462 A CNB2005100471462 A CN B2005100471462A CN 200510047146 A CN200510047146 A CN 200510047146A CN 100434916 C CN100434916 C CN 100434916C
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column
way valve
post
carbon
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CN1928547A (en
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叶芬
孔宏伟
路鑫
叶耀睿
许国旺
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The related analysis process for four-carbon olefin comprises: selecting non-polar solid-phase DC200 as column (1) to fast separate iC5 and four-carbon olefin; using chromatographic column of 0.19%picric acid/Carbopack C as column (2) to separate four-carbon olefin; finally, detecting iC4O, nC4O, iC4=, nC4-1=, tC4-2=, cC4-2=, and 1, and 3C4= =. This invention bases on 'industrial chromatograph analogue system' to provide important data for production conveniently.

Description

A kind of process-scale chromatography flow process and instrumentation thereof of analyzing 4-carbon olefin
Technical field
The present invention relates to analyze the analysis and the 4-carbon olefin industrial process chromatograph of each Main Ingredients and Appearance in the butene-1 production run, specifically a kind of process-scale chromatography flow process and instrumentation thereof of analyzing 4-carbon olefin.
Background technology
The industrial process chromatograph is widely used in on-line analysis in factory in recent years, [document 1:Pecsok R L plays an important role in commercial production, Shieds L D, Cairns T, et al.Modern Methodsof Chemical Analysis.2nd ed.New York; John Wiley ﹠amp; Sons, 1976]; 4-carbon olefin industrial process chromatograph is to be used for analyzing in the processing medium of each conversion zone in the butene-1 production run and control yield and the closely-related key component of product quality, and this produces control and improve productive rate and has very important significance.The AI-100 4-carbon olefin industrial process analyser of Daqing Ethylene industrial group employing at present is made up of 5 root chromatogram columns, 3 transfer valves and a detecting device.Because flow process complexity, outmoded is very difficult in the use debugging; Satisfy the development of producing so need develop new analysis process in time.AI-100 4-carbon olefin industrial process analyser flow process is specific as follows:
(1) chromatogram column system:
Post 1 #25%DC-200/Chromosorb P 60/80 12ft * 1/8in
Post 2 #Phenyl isocyano group ester/Porasil C 80/100 12ft * 3/16in
Post 3 #Special adipate//Chromosorb P 60/80 10ft * 1/8in
Post 4 #Special adipate//Chromosorb P 60/80 10ft * 1/8in
Post 5 #OPN/Porasil C 80/100 15tt * 1/8in
(2) switching flow figure AI-100 switching flow figure as shown in Figure 1.
As can be seen from Figure 1, AI100 is made up of two streams: first stream is by post 1 #, 2 #, 5 # Form post 1 #Be blowback iC 4 =The every other component in back, post 2 #, 5 #Further separate the iC that first stream does not separate fully 4 =And nC 4-1 =
Second stream is by post 3 #, 4 #, 5 # Form post 3 #Be blowback 1,3C 4 ==Back all components, post 4 #, 5 #Further separate iC 4, nC 4, iC 4 =, nC 4-1 =, tC 4-2 =, cC 4-2 =, 1,3C 4 ==Final separate colors spectrogram is seen Fig. 2.
Post 5 #Be shared, valve 3 has the function of stream 1,2 commutations.
This flow process has two problems:
1. this cover chromatographic system not only has many pillars, and comprises a plurality of sampling valves, transfer valve; Because each component movement locus in post is subjected to chromatogram thermodynamics and kinetics combined influence [document 1:Pecsok RL, Shieds L D, Cairns T, et al.Modern Methods of Chemical Analysis.2nd ed.New York; John Wiley ﹠amp; Sons, 1976; Document 2: Xu Guowang, Ye Fen, Lu Xin etc., special on-line chromatograph post production domesticization final report, the evaluation meeting report of Shenyang Branch of the Chinese Academy of Sciences; 2000.10; Document 3: Lu Peizhang, Xu Guowang, expert system of gas chromatography, Shandong science and technology publishing house, Jinan, 1994], very complicated in use debugging work, bring very big difficulty to production division.
2. the stationary phase (phenyl isocyano group ester/Porasil C) of the 2nd post in this cover flow process column system stops production, and former Japanese manufacturer proposes to upgrade this flow process, a large amount of foreign exchange of so just essential consumption.
The applicant is at another piece patent [document 4: Ye Fen, Xu Guowang, Lu Xin etc., a kind of analog system of industrial chromatography, number of patent application: 00123367.X, the patent No.: ZL00123367.X] in introduced with universal gas chromatograph and simulated, the feasibility of exploitation process-scale chromatography flow process, the present invention has developed the new process-scale chromatography flow process of a cover analyzing 4-carbon olefin on this basis, this not only is the production solution problem analytically of butene-1, and be patent [document 4: Ye Fen, Xu Guowang, Lu Xin etc., a kind of analog system of industrial chromatography, number of patent application: 00123367.X, the patent No.: ZL00123367.X] exploitation, the feasibility of developing new chromatographic process provides a strong proof.
Summary of the invention
The object of the present invention is to provide a kind of operating process simple analysis 4-carbon olefin the process-scale chromatography flow process and a kind of simple in structure, use instrumentation easily.
For achieving the above object, the technical solution used in the present invention is:
A kind of process-scale chromatography flow process of analyzing 4-carbon olefin as guard column, is separated iC5 and 4-carbon olefin with non-polar stationary phase DC200 fast entirely; Separate carbon 4 hydrocarbon with chromatographic column 0.19%picric acid/Carbopack C as post, with the iC in chromatographic detector detection carbon 4 hydrocarbon 4 O, nC 4 O, iC 4 =, nC 4-1 =, tC 4-2 =, cC 4-2 =, 1,3C 4 ==
Described post 1 is the 25%DC200/102 of long 1～2m, internal diameter 2～3mm; Post 2 is 0.19%picric acid/Carbopack C of long 4～6m, internal diameter 2～3mm; 102 carriers in the post 1 can be all red zeyssatite carriers like the performance classes.
The instrumentation of the process-scale chromatography flow process of above-mentioned analyzing 4-carbon olefin comprises guard column and chromatographic column, six-way valve A and six-way valve B, hydrogen flame detector (or thermal conductivity detector (TCD)); The 1. position and carrier gas N of described six-way valve A 2Link to each other, 4. the 3. position of six-way valve A reaches, and the position links to each other with outlet with the import of sample respectively, the 6. position of six-way valve A links to each other with the 1. position of six-way valve B, 6. the 2. position of six-way valve B reaches, and the position links to each other with two ports of guard column respectively, the 3. position of six-way valve B links to each other with the entrance point of chromatographic column, the endpiece of chromatographic column leads to hydrogen flame detector, the 4. position and carrier gas N of six-way valve B 2Link to each other, the 5. position of six-way valve B is through emptying behind the resistance gauge.
Advantage of the present invention is: process selecting non-polar stationary phase DC200 of the present invention is as guard column, and it can separate iC5 and 4-carbon olefin fast entirely, reaches the purpose of quick blowback 1, the 3 whole heavy constituent in butadiene back; And the carrier intensity of selecting for use is higher, in switching flow, is suitable for the variation repeatedly of pressure.Post 2 #(0.19%picric acid/Carbopack C) in recent years newly developed, generally acknowledge it is the best dedicated columns of separating carbon 4 hydrocarbon, consequently all stable hydrocarbon of carbon 4 can both well be separated with alkene.Like this with two root chromatogram columns, two six-way valves, a hydrogen flame detector (FID or thermal conductivity detector (TCD) TCD), two action (sample introductions by valve, a blowback) just can finish the total analysis of 7 components of carbon 4 hydrocarbon, because flow process is simple, so debugging, use and to upgrade column system all very easy.With present industrial flow stratographic analysis relatively, the no matter selection of chromatographic column stationary phase, or the design of analysis process, new technological process all shows its rationality and superiority.
Description of drawings
Fig. 1 is AT-100 switching flow figure in the prior art; Wherein 10 is post 1 #, 11 is post 2 #, 12 is post 3 #, 13 posts 4 #, 14 is post 5 #, 5 is hydrogen flame detector, 20 sample inlets, and 21 is carrier gas inlet, and 22 are the carrier gas outlet, and 23 is sample export;
Fig. 2 is that AT-100 analyzes chromatogram in the prior art;
Fig. 3 is the new process flow diagram of AI-100 of the present invention, and wherein 1 is post 1 #, 2 is chromatography column 2 #, 3 is six-way valve A, and 4 is six-way valve B, and 5 is hydrogen flame detector, and 6 is resistance gauge, and Sample in and Sample out are sample inlet and outlet, and Loop is a sample hose, and Vent is emptying, FID (or TCD) is a detecting device;
Fig. 4 is the present invention 01 #Post separating property chromatogram (bitter 5-12);
Fig. 5 is the present invention 02 #Post separating property chromatogram (DC200-6 ,-7);
Fig. 6 is the present invention 03 #Post separating property chromatogram (BB5-4);
Fig. 7 is the present invention 04 #Post separating property chromatogram (OPN54);
Fig. 8 is the present invention 1 #+ TCD+2 #The separate colors spectrogram, chromatographic condition: Shanghai Kechuang chromatographic apparatus company 900 chromatographs; Detecting device TCD; The WSC5.01 of the Chemistry and Physics Institute of Chinese Academy of Sciences data acquisition software; Carrier gas 30ml/min (H 2); 45 ℃ of column temperatures;
Fig. 9 is the present invention 1 #+ 2 #+ TCD separate colors spectrogram; Chromatographic condition: same Fig. 8.
Embodiment
Embodiment:
Carbon 4 industrial process stratographic analyses are widely used in petrochemical complex, it can provide the result of butene-1 production process real-time analysis, provide reliable foundation to control of process condition, aspect this keeps the safety in production, raises the efficiency in assurance important effect is arranged.The carbon 4 industrial process chromatographic processs that adopt are outmoded, loaded down with trivial details at present, use difficulty, are badly in need of upgrading.Chromatogram worker is doing many work aspect the new switching flow of exploitation, but run into very big difficulty: the present invention is at patent " a kind of analog system of industrial chromatography " (number of patent application: 00123367.X, the patent No.: on basis ZL00123367.X), the new carbon 4 hydrocarbon industrial process chromatograms of one cover that adopted the analog chromatogram system development, be used for analyzing in the processing medium of each conversion zone of butene-1 production run and control yield and the closely-related key component of product quality, for commercial production provides important data.
The present invention adopts the single current road flow process of two root chromatogram columns, two six-way valves, a chromatographic detector, by sample introduction, two actions of blowback, just can analyze whole seven components in carbon 4 appropriate hydrocarbon gas;
Process flow diagram is seen shown in Figure 3; As guard column, separate iC5 and 4-carbon olefin with non-polar stationary phase DC200 fast entirely; Separate carbon 4 hydrocarbon with chromatographic column 0.19%picric acid/Carbopack C as post, with the iC in chromatographic detector detection carbon 4 hydrocarbon 4 O, nC 4 O, iC 4 =, nC 4-1 =, tC 4-2 =, cC 4-2 =, 1,3C 4 ==
Concrete structure is as follows:
A kind of instrumentation of process-scale chromatography flow process of analyzing 4-carbon olefin comprises guard column 1 and chromatographic column 2, six-way valve A3 and six-way valve B4, hydrogen flame detector 5; The 1. position and carrier gas N of described six-way valve A3 2Link to each other, 4. the 3. position of six-way valve A3 reaches, and the position links to each other with outlet with the import of sample respectively, the 6. position of six-way valve A3 links to each other with the 1. position of six-way valve B4,6. the 2. position of six-way valve B4 reaches, and the position links to each other with two ports of guard column 1 respectively, the 3. position of six-way valve B4 links to each other with the entrance point of chromatographic column 2, the endpiece of chromatographic column 2 leads to hydrogen flame detector 5, the 4. position and carrier gas N of six-way valve B4 2Link to each other, the 5. position of six-way valve B4 is through a resistance gauge 6 back emptying.
Among Fig. 3 in two six-way valves valve 1 be sampling valve, (solid line is the sampling state, and dotted line is the sample introduction state); Valve 2 is back-flushing valve (valve 2 dotted lines are the blowback state, and solid line is a released state).Chromatographic column 1 #Be the heavy constituent that are used for behind blowback 1,3 butadiene, chromatographic column 2 #Be further to separate all carbon 4 components after the blowback.Serve as to instruct to carry out the recommendation of chromatographic column with document [2,3] at first, the method for introducing with document [4] is estimated chromatographic column and blowback time and is selected again.
(1) selection of chromatographic column
Because the complete optimum chromatographic column of separating of carbon 4 components generally acknowledges it is 0.19%picric acid/CarbopackC, so post 2 #Just selected 0.19%picric acid/Carbopack C, selecting the post task so mainly is exactly to select post 1.
According to document [2,3], be applicable to C 4, C 5The chromatographic column of separating mainly contains 0.19%picric acid/Carbopack C, DC200/102, β β oxygen dipropyl cyanogen/6201, OPN/Porasil C.At first carry out the comparison of these four chromatographic column separating properties with 1.5ft * 1/8in column length.
Chromatographic condition is as follows: Shanghai Kechuang chromatographic apparatus company 900 chromatographs; Detecting device TCD; The WSC of the Dalian Chemistry and Physics Institute of the Chinese Academy of Sciences 5.01 data acquisition softwares; Carrier gas H 240 ℃ of column temperatures; Flow velocity 30ml/min; Chromatographic column is as follows respectively:
01 #Post 0.19%picric acid/Carbopack C 80/100
02 # Post 30%,DC2,00/,102 80/100
03 # Post 30% β β oxygen dipropyl cyanogen/6,201 80/100
04 #Post OPN/Porasil C 80/100
C 1～C 5Analysis of spectra is seen Fig. 4-7.
From Fig. 4～7 more as can be seen: post 1 selects 1.5ft long DC-200 and 0.19%picric acid/Carbopack C can reach quick blowback C 5And the purpose of back component.02 #Not only the blowback interval is narrow for the shortcoming of post, and to go out the peak order be 1,3C 4 ==, tC 4-2 =, cC 4-2 =Go out peak order cC with post 2 4-2 =, tC 4-2 =, 1,3C 4 ==On the contrary, separate for post 2 and bring very big pressure.01 #Identical with the stationary phase of post 2, it is identical to go out the peak order, be favourable from separation angle, and the blowback interval is wide, is easy to control; But its intensity is relatively poor, may influence the life-span of column system, considers flow process center pillar 1 #Be in pressure for a long time repeatedly under the impact of bigger variation, so selection intensity preferably 02 at first #Post is made the post 1 in the flow process, and chromatographic column is suitably extended.
Like this, column system is recommended as follows:
Post 1 #25%,DC2,00/,102 80/100 2m * 1/8
Post 2 #0.19%picric acid/Carbopack C 80/100 4m * 1/8
(2) chromatographic column 1 #Determining of blowback time:
Press post 1 #+ TCD+ post 2 #The mode connected system of series connection, the sample introduction analysis.In 1 delivery time of post, with the time of decision valve blowback, spectrogram as shown in Figure 8 with each component of TCD detector monitors analytic sample.
From spectrogram 8 as can be seen at post 1 # Carbon 4 components go out the cC at peak at last 4-2 =Went out the peak at 140 seconds and finish, 140-175 rotating valve second just can go out chromatogram column system with the whole blowbacks of the component of carbon more than 5 like this.
(3) separate spectrogram at last
To connect detecting device after post 1,2 series connection, the analyzing 4-carbon sample is observed the separate condition of each component.Behind post 1,2, the ultimate analysis spectrogram is seen Fig. 9.
From chromatogram iC as can be seen 4 O, nC 4 O, iC 4 =, nC 4-1 =, tC 4-2 =, cC 4-2 =, 1,3C 4 ==Seven components of all of carbon 4 baseline separation well in 14 minutes satisfies the requirement of technology controlling and process.
Wherein: picric acid/Carbopack C is the commercialization carrier; IC 4 O, nC 4 O, iC 4 =, nC 4-1 =, tC 4-2 =, cC 4-2 =, 1,3C 4 ==Be respectively isobutane, normal butane, isobutylene, n-butene-1, anti-butene-2, maleic-2,1,3 butadiene.60/80, the 80/100 order number that is respectively carrier.
With post 1 #Compare, as can be seen tC 4-2 =, cC 4-2 =, 1,3C 4 ==Go out the peak out of order, thus post when coupling, post 1 #Unsuitable long.Under the condition that carbon 5 can separate, post 1 #Get weak point as far as possible.Equally, flow process is preferably selected two six-way valves for use, and does not select a ten-way valve for use, shortens each component at post 1 as far as possible #The time that stops, be beneficial to tC 4-2 =, cC 4-2 =, 1,3C 4 ==Go out putting upside down of peak order.

Claims (3)

1. the process-scale chromatography method of an analyzing 4-carbon olefin is characterized in that: as pre-column (1), separate iC5 and 4-carbon olefin with non-polar stationary phase 25%DC200 fast entirely; Separate carbon 4 hydrocarbon with chromatographic column 0.19%picricacid/Carbopack C as separating column (2), with the isobutane iC in FID or TCD detection carbon 4 hydrocarbon 4 0, normal butane nC 4 0, isobutylene iC 4 =, n-butene-1nC 4-1 =, anti-butene-2 tC 4-2 =, maleic-2cC 4-2 =, 1,3-butadiene 1,3C 4 =, wherein column temperature uses 40 ℃ or 45 ℃, and the post flow is 30ml/min, and described pre-column (1) is the 25%DC200/102 of long 2m, internal diameter 2～3mm; Separating column (2) is the 0.19%picric acid/Carbopack C of long 4m, internal diameter 2～3mm.
2. according to the process-scale chromatography method of the described analyzing 4-carbon olefin of claim 1, it is characterized in that: 102 carriers in the described pre-column 1 are red zeyssatite carriers.
3. the instrumentation of the process-scale chromatography method of the described analyzing 4-carbon olefin of claim 1 is characterized in that: comprise pre-column (1) and separating column (2), six-way valve A (3) and six-way valve B (4), hydrogen flame detector or thermal conductivity detector (TCD) (5); The 1. position of described six-way valve A (3) links to each other with carrier gas N2 or H2,4. the 3. position of six-way valve A (3) reaches, and the position links to each other with outlet with the import of sample respectively, the 6. position of six-way valve A (3) links to each other with the 1. position of six-way valve B (4), 6. the 2. position of six-way valve B (4) reaches, and the position links to each other with two ports of pre-column (1) respectively, the 3. position of six-way valve B (4) links to each other with the entrance point of separating column (2), the endpiece of separating column (2) leads to hydrogen flame detector or thermal conductivity detector (TCD) (5), the 4. position of six-way valve B (4) links to each other with carrier gas N2 or H2, and the 5. position of six-way valve B (4) is through a resistance gauge (6) back emptying.
CNB2005100471462A 2005-09-07 2005-09-07 Industrial flow for analyzing 4-carbon olefin and dedicated instrument for same Expired - Fee Related CN100434916C (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD282080A5 (en) * 1988-12-30 1990-08-29 Akad Wissenschaften Ddr PROCESS FOR DETERMINING C DEEP 4-CARBON MIXTURES
CN1356547A (en) * 2000-12-06 2002-07-03 中国科学院大连化学物理研究所 Analog system of industrial chromatography

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD282080A5 (en) * 1988-12-30 1990-08-29 Akad Wissenschaften Ddr PROCESS FOR DETERMINING C DEEP 4-CARBON MIXTURES
CN1356547A (en) * 2000-12-06 2002-07-03 中国科学院大连化学物理研究所 Analog system of industrial chromatography

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GAS CHROMATOGRAPHIC SEPARATION OF ALLC1-C4 HYDROCARBONS BY MULTI-SUBSTRATEGAS-SOLID-LIQUID CHROMATOGRAPHY. W.K.AL-THAMIR etal.Journal of Chromatography,Vol.142 . 1977 *
多维气相色谱在线分析轻烃芳构化产物的研究. 李孝国等.石油化工高等学校学报，第17卷第2期. 2004 *

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