CN111796037A - Method for detecting caprolactam industrial ammoximation reaction liquid - Google Patents
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Abstract
The invention provides a method for detecting caprolactam industrial ammoximation reaction liquid. The method comprises the steps of firstly carrying out idle running pretreatment on a chromatograph equipped with a strong-polarity chromatographic column, and then respectively detecting the ammoximation reaction liquid and the circulating tertiary butanol by using a gradient heating scheme. The method can realize effective separation of each impurity in the ammoximation reaction liquid, eliminate the interference of circulating impurities in the tert-butyl alcohol as a medium, realize accurate content detection of reaction impurities, accurately determine the effective conversion rate of the ammoximation reaction, accurately evaluate the effect of the ammoximation reaction and have good reproducibility of detection results.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a detection method of caprolactam industrial ammoximation reaction liquid.
Background
Caprolactam is an important material in the current organic chemical production, and industrial caprolactam can be used for producing nylon fibers, engineering plastics, synthetic drugs and the like. The cyclohexanone ammoximation method is a process method for producing caprolactam, and the main process flow of the cyclohexanone ammoximation method is that cyclohexanone is subjected to ammoximation reaction with ammonia and hydrogen peroxide in a tert-butyl alcohol medium to generate cyclohexanone oxime; the cyclohexanone oxime undergoes Beckmann rearrangement to caprolactam.
The ammoximation reaction is an important reaction of a caprolactam process, and the detection of components of a liquid material (hereinafter referred to as a reaction solution) after the ammoximation reaction becomes an important basis for evaluating the reaction effect. Impurities in the ammoximation reaction liquid are mostly polar organic matter impurities, the industry detection adopts a weak-polarity chromatographic column, the effective separation of the impurities in the reaction liquid cannot be realized by the chromatographic column, and the composition of the reaction liquid cannot be accurately detected. In addition, the reaction impurity composition in the reaction liquid is complex, the molecular weight and boiling point range of the impurity are widely distributed, and effective separation and content determination of the reaction liquid impurity cannot be realized by single gradient temperature-rising chromatographic detection. In addition, in industrial production, the reaction medium, i.e., tert-butyl alcohol, is recycled, so that reaction impurities are continuously accumulated in the reaction solution, the measurement of the true content of the impurities in the reaction solution is interfered, and the effective conversion condition (hereinafter, referred to as effective conversion rate) of the raw material, i.e., cyclohexanone, in the ammoximation reaction solution cannot be accurately known. In addition, due to the participation of hydrogen peroxide and ammonia in the ammoximation reaction, the reaction liquid is alkaline and contains more water, so that the peak of chromatographic detection impurities is easy to fluctuate, and the detection result has poor reproducibility.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to establish a detection method of caprolactam industrial ammoximation reaction liquid, which can realize the effective separation of each impurity in the ammoximation reaction liquid, can eliminate the interference of circulating impurities in medium tertiary butanol, can realize the accurate content detection of reaction impurities, can accurately determine the effective conversion rate of the ammoximation reaction, can accurately evaluate the ammoximation reaction effect and has good reproducibility of the detection result.
Therefore, the invention provides a method for detecting a caprolactam industrial ammoximation reaction liquid, which comprises the steps of firstly carrying out idle running pretreatment on a chromatograph equipped with a strong-polarity chromatographic column, and then respectively detecting the ammoximation reaction liquid and circulating tertiary butanol by using a gradient heating scheme.
In the method of the present invention, preferably, the strongly polar chromatography column may be an HP-INNOWAX chromatography column, more preferably, HP-INNOWAX 60m 0.32mm 0.25 μm, HP-INNOWAX 60m 0.32mm 0.5 μm, HP-INNOWAX 60m 0.25mm 0.5 μm, etc., and the flow rate of the carrier gas in the chromatography column may be 0.5 to 4 ml/min.
In the method of the present invention, preferably, the gradient heating-up scheme may be an N-gradient chromatography detection gradient heating-up scheme, where N is greater than or equal to 2. Preferably, the gradient temperature-rising scheme for the N-gradient chromatography detection is as follows: a gradient temperature-rise scheme of N-2, wherein the initial temperature is 30-100 ℃, the temperature is kept for 1-20min, the temperature is raised to 110-180 ℃ at the speed of 2-20 ℃/min, the temperature is kept for 1-10min, the temperature is raised to 190-220 ℃ at the speed of 2-20 ℃/min, and the temperature is kept for 1-10 min; or the following steps: the temperature is increased to 30-80 ℃ at the initial temperature, kept for 1-20min, increased to 90-120 ℃ at the speed of 2-20 ℃/min, kept for 1-20min, increased to 180 ℃ at the speed of 2-20 ℃/min, kept for 1-10min, increased to 220 ℃ at the speed of 190 ℃ at the speed of 2-20 ℃/min, and kept for 1-10 min.
In the method of the invention, preferably, the sample inlet temperature is selected to be 260-.
In the method of the invention, preferably, a hydrogen flame ionization FID detector is selected, the detector temperature is 280-320 ℃, the detector hydrogen flow rate is 30-40ml/min, and the detector air flow rate is 300-400 ml/min.
In the method of the present invention, preferably, a method of calculating the effective conversion rate of the reaction clear solution after subtracting the content of the circulating impurities in the tert-butyl alcohol medium is selected. The calculation formula for the effective conversion is as follows:
in the method, a comprehensive chromatographic detection scheme combining a chromatographic pretreatment method and a reaction liquid detection chromatographic method is selected, namely, the chromatographic pretreatment method is operated before the reaction liquid is subjected to chromatographic detection.
In the method of the present invention, preferably, the chromatographic setting parameters of the pretreatment method are selected as follows: the initial temperature is 30-100 ℃, the temperature is kept for 1-10min, the temperature is raised to 190-220 ℃ at the speed of 1-20 ℃/min, and the temperature is kept for 1-10 min.
Compared with the prior art, the invention has the advantages that:
the method adopts the strong-polarity chromatographic column to detect the reaction liquid, and can effectively separate the polar reaction impurities in the reaction liquid;
the invention adopts a multi-gradient chromatographic detection gradient heating scheme, and can separate more reaction impurities in the reaction solution;
the invention adopts a calculation method for determining the effective conversion rate of the reaction liquid by deducting the content of the circulating impurities in the tert-butyl alcohol medium, can accurately determine the effective conversion rate of the ammoximation reaction, and can accurately evaluate the effect of the ammoximation reaction.
The invention adopts a comprehensive chromatographic detection scheme comprising a pretreatment method, can eliminate the interference of more alkaline and water-containing reaction liquid on chromatographic determination, can ensure stable impurity peak appearance of chromatographic detection and has good reproducibility of detection results.
Drawings
FIG. 1 is a gas phase detection chromatogram of the reaction solution of example 1.
FIG. 2 is a gas phase detection chromatogram of the reaction solution of example 2.
FIG. 3 is a gas detection chromatogram of the reaction solution of example 3.
FIG. 4 is a gas phase detection chromatogram of the reaction solution of comparative example 1.
Detailed Description
The present invention is illustrated by the following examples, but the present invention is not limited to the following examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Device
An Agilent 8890 gas chromatograph equipped with a split injection port and an FID detector; the gas for chromatographic detection is high-purity hydrogen, high-purity nitrogen and pure air.
Reagent
Ammoximation reaction liquid; the tert-butanol medium is recycled.
Example 1
The assay was performed using a chromatograph equipped with an HP-INNOWAX 60m 0.32mm 0.25 μm column. Firstly, the pretreatment method is used for treating the chromatography in idle running (without sample injection), and then the gradient heating scheme is immediately used for respectively detecting the ammoximation reaction solution and the circulating tertiary butanol. The chromatographic detection conditions are that the temperature of a sample inlet is 260 ℃, the split ratio is 30:1, and the sample injection amount is 0.5 mu L; the detector temperature is 280 ℃, the detector hydrogen flow is 30ml/min, and the detector air flow is 300 ml/min; the flow rate of the carrier gas in the chromatographic column is 1 ml/min. In this example, the pretreatment method was used for chromatographic conditions with an initial temperature of 40 ℃ for 1min, and the temperature was raised to 200 ℃ at 20 ℃/min for 1 min. In this embodiment, a gradient temperature increasing scheme of N ═ 2 is adopted, the initial temperature is 40 ℃, the temperature is maintained for 15min, the temperature is increased to 110 ℃ at 10 ℃/min, the temperature is maintained for 10min, the temperature is increased to 200 ℃ at 10 ℃/min, and the temperature is maintained for 10 min.
The gas phase detection chromatogram of the obtained reaction solution is shown in FIG. 1. Through detection, 18 reaction impurities are separated from the reaction liquid, and the separation of each impurity is good.
Detecting the content of each substance in the reaction liquid through gas chromatography of the reaction liquid, wherein the content of the cyclohexanone oxime is 18.3228%; the cyclohexanone content is 0.0100%; the content of tertiary butanol is 44.6252%; the reaction impurity content was 0.0664%. The content of circulating impurities in the tert-butyl alcohol medium is 0.0145% by circulating tert-butyl alcohol gas chromatography detection.
The content of impurities detected in the circulating tert-butanol was subtracted from the detection result of the reaction solution according to the following equation, and the effective conversion of the reaction solution was calculated to be 99.62%.
And the difference between two parallel results is less than 0.01 percent after the parallel measurement is carried out for a plurality of times, which indicates that the repeatability of the detection result is good.
Example 2
The assay was performed using a chromatograph equipped with an HP-INNOWAX 60m 0.32mm 0.5 μm column. Firstly, the pretreatment method is used for treating the chromatography in idle running (without sample injection), and then the gradient heating scheme is immediately used for respectively detecting the ammoximation reaction solution and the circulating tertiary butanol. The chromatographic detection conditions are that the temperature of a sample inlet is 260 ℃, the split ratio is 30:1, and the sample injection amount is 0.5 mu L; the detector temperature is 280 ℃, the detector hydrogen flow is 30ml/min, and the detector air flow is 300 ml/min; the flow rate of the carrier gas in the chromatographic column is 1 ml/min. In this example, the pretreatment method was used for chromatography at an initial temperature of 35 ℃ for 2min, and the temperature was raised to 200 ℃ at 15 ℃/min for 2 min. In this embodiment, a gradient temperature increasing scheme with N ═ 3 is adopted, the initial temperature is 35 ℃, the temperature is maintained for 10min, the temperature is increased to 110 ℃ at 10 ℃/min, the temperature is maintained for 10min, the temperature is increased to 160 ℃ at 10 ℃/min, the temperature is maintained for 10min, the temperature is increased to 200 ℃ at 10 ℃/min, and the temperature is maintained for 10 min.
The gas phase detection chromatogram of the obtained reaction solution is shown in FIG. 2. Through detection, 20 reaction impurities are separated from the reaction liquid, and the separation of each impurity is good.
Detecting the content of each substance in the reaction liquid through gas chromatography of the reaction liquid, wherein the content of the cyclohexanone oxime is 18.3191%; the cyclohexanone content is 0.0100%; the content of tertiary butanol is 44.6252%; the reaction impurity content was 0.0701%. The content of circulating impurities in the tert-butyl alcohol medium is 0.0145% by circulating tert-butyl alcohol gas chromatography detection.
The content of impurities detected in the circulating tert-butanol was subtracted from the reaction solution detection result according to the following equation, and the effective conversion rate of the reaction solution was calculated to be 99.60%.
And the difference between two parallel results is less than 0.01 percent after the parallel measurement is carried out for a plurality of times, which indicates that the repeatability of the detection result is good.
Example 3
The assay was performed using a chromatograph equipped with an HP-INNOWAX 60m 0.25mm 0.5 μm column. Firstly, the pretreatment method is used for treating the chromatography in idle running (without sample injection), and then the gradient heating scheme is immediately used for respectively detecting the ammoximation reaction solution and the circulating tertiary butanol. The chromatographic detection conditions are that the temperature of a sample inlet is 300 ℃, the split ratio is 50:1, and the sample volume is 1 mu L; the detector temperature is 300 ℃, the detector hydrogen flow is 40ml/min, and the detector air flow is 400 ml/min; the flow rate of the carrier gas in the chromatographic column is 2 ml/min. In this example, the pretreatment method was used for chromatographic conditions, with an initial temperature of 30 ℃ and a hold time of 1min, and the temperature was raised to 220 ℃ at a rate of 20 ℃/min and held for 1 min. In this embodiment, a gradient temperature increasing scheme with N ═ 3 is adopted, the initial temperature is 30 ℃, the temperature is maintained for 10min, the temperature is increased to 90 ℃ at 8 ℃/min, the temperature is maintained for 12min, the temperature is increased to 150 ℃ at 15 ℃/min, the temperature is maintained for 8min, the temperature is increased to 220 ℃ at 15 ℃/min, and the temperature is maintained for 10 min.
The gas phase detection chromatogram of the obtained reaction solution is shown in FIG. 3. Through detection, 21 reaction impurities are separated from the reaction liquid, and the separation of each impurity is good.
Detecting the content of each substance in the reaction liquid through gas chromatography of the reaction liquid, wherein the content of the cyclohexanone oxime is 18.3154%; the cyclohexanone content is 0.0100%; the content of tertiary butanol is 44.6252%; the reaction impurity content was 0.0738%. The content of circulating impurities in the tert-butyl alcohol medium is 0.0145% by circulating tert-butyl alcohol gas chromatography detection.
The content of impurities detected in the circulating tert-butanol was subtracted from the detection result of the reaction solution according to the following equation, and the effective conversion rate of the reaction solution was calculated to be 99.58%.
And the difference between two parallel results is less than 0.01 percent after the parallel measurement is carried out for a plurality of times, which indicates that the repeatability of the detection result is good.
Comparative example 1
The comparative example does not adopt a strong polarity chromatographic column, does not detect and deduct circulating impurities in the circulating tertiary butanol, does not adopt a multi-gradient heating scheme, and does not use a pretreatment method to treat the chromatographic empty operation (without sample injection) before analyzing the sample. The specific settings are as follows:
the reaction solution was analyzed by using HP-5 (5% -phenyl) -methylpolysiloxane 60m 0.32mm 0.25 μm weakly polar chromatography column. The chromatographic detection conditions are that the temperature of a sample inlet is 260 ℃, the split ratio is 30:1, and the sample injection amount is 0.5 mu L; the detector temperature is 280 ℃, the detector hydrogen flow is 30ml/min, and the detector air flow is 300 ml/min; the flow rate of the carrier gas in the chromatographic column is 1 ml/min. In this embodiment, a one-time heating scheme is adopted, the initial temperature is 70 ℃, the temperature is maintained for 15min, and the temperature is increased to 150 ℃ at a speed of 10 ℃/min, and the temperature is maintained for 10 min.
The gas phase detection chromatogram of the obtained reaction solution is shown in FIG. 4. Through detection, 10 reaction impurities are separated out from the reaction liquid, the number of the impurities is obviously reduced, and partial polar impurities are not separated out.
Detecting the content of each substance in the reaction liquid through gas chromatography of the reaction liquid, wherein the content of the cyclohexanone oxime is 18.4268%; the cyclohexanone content is 0.0100%; the reaction impurity content was 0.0252%.
The effective conversion of the reaction solution was calculated to be 99.81% according to the following equation.
And the difference between two parallel results is more than 0.01 percent when the measurement is carried out for multiple times in parallel, which indicates that the repeatability of the detection result is poor and the data is seriously distorted.
The above description is for the purpose of illustrating the present invention and is not intended to limit the scope of the present invention, and any person skilled in the art can substitute or change the technical solution of the present invention and its conception within the technical scope of the present invention, and the technical solution and the concept of the present invention are also intended to be covered by the scope of the claims of the present invention.
Claims (7)
1. A method for detecting a caprolactam industrial ammoximation reaction liquid comprises the steps of firstly carrying out idle running pretreatment on a chromatograph equipped with a strong-polarity chromatographic column, and then respectively detecting the ammoximation reaction liquid and circulating tertiary butanol by using a gradient heating scheme.
2. Method according to claim 1, wherein the strongly polar chromatography column is an HP-INNOWAX chromatography column, preferably an HP-INNOWAX 60m 0.32mm 0.25 μm, HP-INNOWAX 60m 0.32mm 0.5 μm or HP-INNOWAX 60m 0.25mm 0.5 μm, preferably the chromatography column has a carrier gas flow of 0.5-4 ml/min.
3. The method of claim 1 or 2, wherein the gradient warming protocol is an N-gradient chromatography detection gradient warming protocol, wherein N.gtoreq.2; preferably, the gradient temperature-rising scheme for the N-gradient chromatography detection is as follows: a gradient temperature-rise scheme of N-2, wherein the initial temperature is 30-100 ℃, the temperature is kept for 1-20min, the temperature is raised to 110-180 ℃ at the speed of 2-20 ℃/min, the temperature is kept for 1-10min, the temperature is raised to 190-220 ℃ at the speed of 2-20 ℃/min, and the temperature is kept for 1-10 min; or the following steps: the temperature is increased to 30-80 ℃ at the initial temperature, kept for 1-20min, increased to 90-120 ℃ at the speed of 2-20 ℃/min, kept for 1-20min, increased to 180 ℃ at the speed of 2-20 ℃/min, kept for 1-10min, increased to 220 ℃ at the speed of 190 ℃ at the speed of 2-20 ℃/min, and kept for 1-10 min.
4. The method as claimed in claim 1 or 2, wherein the injection port temperature is 260 ℃ and 300 ℃, the split ratio is 30-60:1, and the injection amount is 0.5-1 μ L.
5. The method as claimed in claim 1 or 2, wherein a hydrogen flame ionization FID detector is used, the detector temperature is 280-320 ℃, the detector hydrogen flow is 30-40ml/min, and the detector air flow is 400 ml/min.
6. The method of claim 1 or 2, wherein the effective conversion%
7. The method of claim 1 or 2, wherein the pre-processed chromatographic setting parameters are: the initial temperature is 30-100 ℃, the temperature is kept for 1-10min, the temperature is raised to 190-220 ℃ at the speed of 1-20 ℃/min, and the temperature is kept for 1-10 min.
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| CN101117323A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Preparation method of cyclohexanone oxime |
| US20120078014A1 (en) * | 2010-09-27 | 2012-03-29 | Sumitomo Chemical Company, Limited | Method for manufacturing cyclohexanone oxime |
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| CN101117323A (en) * | 2006-07-31 | 2008-02-06 | 中国石油化工股份有限公司 | Preparation method of cyclohexanone oxime |
| US20120078014A1 (en) * | 2010-09-27 | 2012-03-29 | Sumitomo Chemical Company, Limited | Method for manufacturing cyclohexanone oxime |
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Application publication date: 20201020 |