Quantitative analysis method for tert-butyl hydroperoxide synthesis reaction feed liquid
By using gas chromatography with 2-hexanol as an internal standard, the accuracy and efficiency problems of quantitative analysis of tert-butyl hydrogen peroxide synthesis reaction solution in the prior art have been solved, and rapid and accurate determination of component content has been achieved.
Patent Information
- Application Number
- CN202511841693.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-09
- Publication Date
- 2026-02-06
AI Technical Summary
Existing quantitative analysis methods cannot accurately determine the content of each component in the reaction solution for the synthesis of tert-butyl hydrogen peroxide, and they also suffer from unstable test results and long processing times.
Using 2-hexanol as an internal standard, combined with gas chromatography, the contents of tert-butyl hydroperoxide, tert-butanol, and di-tert-butyl hydroperoxide were calculated by plotting a relative correction factor standard curve, and quantitative analysis was performed using an FID detector and specific chromatographic conditions.
It enables rapid and accurate determination of the content of main products, by-products and raw materials in the feed liquid under the same detection conditions. The method is simple, has good repeatability, and the detection results are highly accurate.
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Figure CN121476470A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of quantitative analysis, and particularly relates to a quantitative analysis method of a tert-butyl hydrogen peroxide synthesis reaction liquid. BACKGROUND
[0002] Tert-butyl hydrogen peroxide (TBHP) is a typical alkyl peroxide, which is extremely sensitive to solvents, acids, bases, metal ions and other pollutants, and is widely used in the field of polymer material preparation. It is an important raw material and intermediate of most organic peroxides, such as crosslinking agents for unsaturated polyesters. At present, TBHP is mainly synthesized by tert-butyl alcohol (TBA) peroxide method. However, although the tert-butyl alcohol peroxide method has a simple process, a relatively short reaction time and low equipment requirements, the by-product di-tert-butyl peroxide (DTBP) is generated in the side reaction, which affects the product quality; at the same time, the reaction is prone to thermal runaway, leading to accidents. Therefore, it is extremely important to control the content of the by-product di-tert-butyl peroxide in the tert-butyl alcohol peroxide method reaction.
[0003] At present, the industry mainly uses iodometric method, gas chromatography external standard method and high performance liquid chromatography derivatization method for quantitative analysis of organic peroxides. There are by-products and unreacted raw materials in the reaction liquid after synthesis reaction, and the iodometric method analysis (Zhu H, Yan J, Zhang Z, et al. Kinetics study of the peroxidation of tert-butyl alcohol to tert-butyl hydrogen peroxide in a microreactor[J]. Organic Process Research & Development, 2023, 28(5): 1486-1493.) will calculate the by-products and unreacted raw materials into tert-butyl hydrogen peroxide, and cannot accurately determine the content of each component in the organic peroxide.
[0004] The defect of the gas chromatography external standard method quantitative analysis lies in that the accuracy of the test result mainly depends on the reproducibility of the sample injection amount and the stability of the operating conditions, and the corresponding calibration curve needs to be determined before each test. Therefore, in actual analysis, the gas chromatography external standard method is relatively time-consuming, and the accuracy of the quantitative analysis of easily decomposed peroxides is not high.
[0005] High performance liquid chromatography derivatization method (Ma Y, Luo X Y, Yuan X, et al. Determination of tert-butyl hydroperoxide by normal phase high performance liquid chromatography [J]. Petroleum and Chemical Industry, 2012, 41(09): 1077-1080; Wang L T, Dong S Q, Zhang Z X, et al. Determination of tert-butyl hydroperoxide in tert-butyl hydroperoxide by high performance liquid chromatography [C]. Qinghai and Ningxia Chromatography Center, Chromatography Committee of Gansu Province. The Seventh Chromatography Academic Report in Northwest and the Twelfth Chromatography Annual Meeting in Gansu Province. Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Graduate School of Chinese Academy of Sciences, 2012: 171.) is to generate new substances by derivatization reaction of peroxide in the reaction tube, and then determined by ultraviolet detection. The defect of high performance liquid chromatography derivatization method is that the derivatization period is long, and the derivatization proportion of different peroxides is biased, it is difficult to accurately quantify the intermediates in the peroxidation process by derivatization method, and it is not suitable for reaction process monitoring and content analysis of complex components.
[0006] Therefore, the existing quantitative analysis method of organic peroxide is not suitable for quantitative analysis of tert-butyl hydroperoxide synthesis reaction liquid, and it is urgent to develop a quantitative analysis method which can stably test the content of each component in tert-butyl hydroperoxide synthesis reaction liquid and eliminate the influence of unstable factors. SUMMARY
[0007] The purpose of the present application is to provide a quantitative analysis method for tert-butyl hydroperoxide synthesis reaction liquid to overcome the shortcomings of the prior art.
[0008] In order to achieve the above purpose of the application, the present application provides the following technical scheme: The present application provides a quantitative analysis method for tert-butyl hydroperoxide synthesis reaction liquid, comprising the following steps: 1) Put the internal standard 2-hexanol into a volumetric flask, and dilute with methanol to obtain an internal standard solution; 2) Mix the tert-butyl hydroperoxide synthesis reaction liquid and the internal standard solution, and perform gas chromatography detection, and calculate the content of tert-butyl hydroperoxide, tert-butyl alcohol and di-tert-butyl hydroperoxide in the tert-butyl hydroperoxide synthesis reaction liquid according to the peak area and the relative correction factor standard curve.
[0009] As a preferred, the relative correction factor standard curve comprises tert-butyl hydroperoxide relative correction factor standard curve, tert-butyl alcohol relative correction factor standard curve and di-tert-butyl hydroperoxide relative correction factor standard curve.
[0010] As a preferred, the drawing method of the tert-butyl hydroperoxide relative correction factor standard curve comprises the following steps: ① Place different masses of tert-butyl hydrogen peroxide standard into volumetric flasks, add internal standard solution, and dilute to volume with methanol to obtain tert-butyl hydrogen peroxide standard solutions of different concentrations. ② Gas chromatography was used to detect tert-butyl hydrogen peroxide standard solutions of different concentrations. The relative correction factor standard curve of tert-butyl hydrogen peroxide was plotted with the mass ratio of tert-butyl hydrogen peroxide to internal standard as the abscissa and the peak area ratio of tert-butyl hydrogen peroxide to internal standard as the ordinate.
[0011] Preferably, the method for plotting the standard curve of the relative correction factor of tert-butanol includes the following steps: a) Place different masses of tert-butanol standards into volumetric flasks, add internal standard solution, and dilute to volume with methanol to obtain tert-butanol standard solutions of different concentrations. b) Gas chromatography was used to detect tert-butanol standard solutions of different concentrations. The relative correction factor standard curve of tert-butanol was plotted with the mass ratio of tert-butanol to internal standard as the abscissa and the peak area ratio of tert-butanol to internal standard as the ordinate.
[0012] Preferably, the method for plotting the standard curve of the relative correction factor of di-tert-butyl hydroperoxide includes the following steps: A) Different masses of di-tert-butyl hydrogen peroxide standard were placed in volumetric flasks, internal standard solution was added, and the volume was adjusted with methanol to obtain di-tert-butyl hydrogen peroxide standard solutions of different concentrations. B) Gas chromatography was used to detect di-tert-butyl peroxide standard solutions of different concentrations. The relative correction factor standard curve of di-tert-butyl peroxide was plotted with the mass ratio of di-tert-butyl peroxide to internal standard as the abscissa and the peak area ratio of di-tert-butyl peroxide to internal standard as the ordinate.
[0013] Preferably, the detector used for gas chromatography detection is an FID detector, and the chromatographic conditions for gas chromatography detection are as follows: Chromatographic column: DB-1701, 30m × 0.32mm × 0.25μm Carrier gas flow rate: 0.5~1.5 mL / min Vaporization chamber temperature: 100~120℃ Detector temperature: 220~240℃ Flow split ratio: 43~47:1 Injection volume: 0.5~1.5μL Column oven temperature: 35~45℃, hold for 10 minutes Heating rate: 8~12℃ / min, heating up to 140℃.
[0014] The beneficial effects of this invention are: The application takes 2-hexanol as an internal standard substance to quantitatively analyze the t-butyl hydroperoxide synthesis reaction liquid by gas chromatography internal standard method, and the content of the main product t-butyl hydroperoxide, the byproduct di-t-butyl hydroperoxide and the raw material t-butanol in the liquid can be obtained under the same detection conditions, the method is safe and efficient, the steps are simple and fast, the detection result is high in accuracy and good in repeatability. BRIEF DESCRIPTION OF DRAWINGS
[0015] Figure 1 is a relative correction factor standard curve of t-butyl hydroperoxide; Figure 2 is a relative correction factor standard curve of di-t-butyl hydroperoxide; Figure 3 is a relative correction factor standard curve of t-butanol; Figure 4 is a gas chromatogram of t-butyl hydroperoxide synthesis reaction liquid; Figure 5 is a flow diagram of a continuous t-butyl hydroperoxide synthesis reaction; Figure 6 is a gas chromatogram of t-butyl hydroperoxide standard solution with a concentration of 21.5 mg / mL in Example 1; Figure 7 is a gas chromatogram of di-t-butyl hydroperoxide standard solution with a concentration of 1.55 mg / mL in Example 1; Figure 8 is a gas chromatogram of t-butanol standard solution with a concentration of 1.18 mg / mL in Example 1; Figure 9 is a gas chromatogram of the first gas chromatography detection of the mixed standard solution mixed with the internal standard substance 2-hexanol; Figure 10 is a gas chromatogram of t-butyl hydroperoxide standard solution in Comparative Example 1. DETAILED DESCRIPTION
[0016] The application provides a quantitative analysis method of t-butyl hydroperoxide synthesis reaction liquid, comprising the following steps: 1) Put the internal standard substance 2-hexanol into a volumetric flask, and dilute with methanol to obtain an internal standard solution; 2) Mix the t-butyl hydroperoxide synthesis reaction liquid and the internal standard solution, and perform gas chromatography detection, and calculate the content of t-butyl hydroperoxide, t-butanol and di-t-butyl hydroperoxide in the t-butyl hydroperoxide synthesis reaction liquid according to the peak area and the relative correction factor standard curve.
[0017] In the present application, the mixing in step 2) preferably further comprises adding an internal standard 2-hexanol into the raw material system of the continuous tert-butyl hydroperoxide synthesis reaction, and then sampling the continuous synthesis reaction liquid for gas chromatography detection. This method can be used for quantitative analysis of the continuous reaction liquid of the tert-butyl hydroperoxide synthesis reaction.
[0018] In the present application, the concentration of the internal standard solution is preferably 40-60 mg / mL, and further preferably 50 mg / mL.
[0019] In the present application, the relative correction factor standard curve preferably comprises a tert-butyl hydroperoxide relative correction factor standard curve, a tert-butyl alcohol relative correction factor standard curve, and a di-tert-butyl hydroperoxide relative correction factor standard curve.
[0020] In the present application, the method for drawing the tert-butyl hydroperoxide relative correction factor standard curve preferably comprises the following steps: ①Different amounts of tert-butyl hydroperoxide standard were placed in volumetric flasks, internal standard solution was added, and methanol was used for constant volume to obtain different concentrations of tert-butyl hydroperoxide standard solution; ②The different concentrations of tert-butyl hydroperoxide standard solution were detected by gas chromatography, with the mass ratio of tert-butyl hydroperoxide to internal standard as the abscissa and the peak area ratio of tert-butyl hydroperoxide to internal standard as the ordinate, and the tert-butyl hydroperoxide relative correction factor standard curve was drawn.
[0021] In the present application, in the different concentrations of tert-butyl hydroperoxide standard solution, the concentration of tert-butyl hydroperoxide is preferably 1-100 mg / mL, further preferably 5-80 mg / mL, and more preferably 7-50 mg / mL; the concentration of the internal standard is preferably 5-15 mg / mL, further preferably 8-12 mg / mL, and more preferably 10 mg / mL.
[0022] In the present application, the method for drawing the tert-butyl alcohol relative correction factor standard curve preferably comprises the following steps: a) Different amounts of tert-butyl alcohol standard were placed in volumetric flasks, internal standard solution was added, and methanol was used for constant volume to obtain different concentrations of tert-butyl alcohol standard solution; b) The different concentrations of tert-butyl alcohol standard solution were detected by gas chromatography, with the mass ratio of tert-butyl alcohol to internal standard as the abscissa and the peak area ratio of tert-butyl alcohol to internal standard as the ordinate, and the tert-butyl alcohol relative correction factor standard curve was drawn.
[0023] In the present application, the concentration of tert-butyl alcohol in the different concentrations of tert-butyl alcohol standard solution is preferably 0.05-5.0 mg / mL, further preferably 0.1-3.5 mg / mL, and more preferably 0.5-2.5 mg / mL; and the concentration of the internal standard is preferably 5-15 mg / mL, further preferably 8-12 mg / mL, and more preferably 10 mg / mL.
[0024] In the present application, the method for drawing the di-tert-butyl hydrogen peroxide relative correction factor standard curve preferably comprises the following steps: A) different amounts of di-tert-butyl hydrogen peroxide standard are placed in a volumetric flask, internal standard solution is added, and methanol is used to make up the volume to obtain di-tert-butyl hydrogen peroxide standard solutions of different concentrations; B) the di-tert-butyl hydrogen peroxide standard solutions of different concentrations are respectively detected by gas chromatography, the mass ratio of di-tert-butyl hydrogen peroxide to internal standard is taken as the abscissa, and the peak area ratio of di-tert-butyl hydrogen peroxide to internal standard is taken as the ordinate, and a di-tert-butyl hydrogen peroxide relative correction factor standard curve is drawn.
[0025] In the present application, the concentration of di-tert-butyl hydrogen peroxide in the different concentrations of di-tert-butyl hydrogen peroxide standard solution is preferably 0.1-10 mg / mL, further preferably 0.2-8 mg / mL, and more preferably 0.5-5 mg / mL; and the concentration of the internal standard is preferably 5-15 mg / mL, further preferably 8-12 mg / mL, and more preferably 10 mg / mL.
[0026] In the present application, the detector for gas chromatography detection is preferably an FID detector, and the chromatographic conditions for gas chromatography detection are preferably as follows: Chromatographic column: DB-1701, 30 m x 0.32 mm x 0.25 μm; Carrier gas flow rate: 0.5-1.5 mL / min, further preferably 0.8-1.2 mL / min, and more preferably 1 mL / min; Gasification chamber temperature: 100-120℃, further preferably 105-115℃, and more preferably 110℃; Detector temperature: 220-240℃, further preferably 225-235℃, and more preferably 230℃; Split ratio: 43-47:1, further preferably 44-46:1, and more preferably 45:1; Injection volume: 0.5-1.5 μL, further preferably 0.8-1.2 μL, and more preferably 1 μL; Column oven temperature: 35-45℃, maintained for 10 min, further preferably 38-42℃, and more preferably 40℃; The temperature rising rate is 8-12℃ / min, preferably 9-11℃ / min, and more preferably 10℃ / min.
[0027] The technical solutions provided by the present application are described in detail below in combination with examples, but they should not be understood as limiting the scope of protection of the present application.
[0028] The process for synthesizing the tert-butyl hydroperoxide reaction solution in the examples and comparative examples of the present application is as follows: 50% hydrogen peroxide solution (0.66 mol of hydrogen peroxide) and 98% sulfuric acid (0.055 mol of H2SO4) are added to a 100 mL reactor, the temperature is raised to 50℃, and 0.33 mol of tert-butyl alcohol (purity 99%) is added dropwise to the reactor over a period of 90 min. After the addition is completed, the reaction is maintained for 3 h, and a tert-butyl hydroperoxide reaction solution is obtained.
[0029] The detector for gas chromatography detection in the examples and comparative examples of the present application is an FID detector, and the chromatography conditions are as follows: chromatography column DB-1701, 30m x 0.32mm x 0.25μm, carrier gas flow rate 1mL / min, vaporization chamber temperature 110℃, detector temperature 230℃, split ratio 45:1, sample injection volume 1μL, column oven temperature 40℃ for 10 min, and temperature rising rate 10℃ / min to 140℃.
[0030] Example 1
[0031] 5.01g of internal standard 2-hexanol is weighed into a 100 mL volumetric flask, dissolved with methanol, and shaken to obtain an internal standard solution.
[0032] 5 portions of tert-butyl hydroperoxide standard (70% mass concentration) are weighed into 10 mL volumetric flasks, 2 mL of the internal standard solution is added, dissolved with methanol, and shaken to obtain tert-butyl hydroperoxide standard solutions with concentrations of 7.6mg / mL, 15.0mg / mL, 21.5mg / mL, 37.2mg / mL, and 49.1mg / mL, respectively, and the concentration of the internal standard is 10.02mg / mL in each solution.
[0033] 5 portions of di-tert-butyl hydroperoxide standard (97% purity) are weighed into 10 mL volumetric flasks, 2 mL of the internal standard solution is added, dissolved with methanol, and shaken to obtain di-tert-butyl hydroperoxide standard solutions with concentrations of 0.52mg / mL, 1.08mg / mL, 1.55mg / mL, 3.43mg / mL, and 4.81mg / mL, respectively, and the concentration of the internal standard is 10.02mg / mL in each solution.
[0034] Take 5 parts of tert-butyl alcohol standard (purity 99%) respectively into 10 mL volumetric flask, add 2 mL of internal standard solution, and then dilute to the mark with methanol, shake well to obtain the standard solution of tert-butyl alcohol with concentrations of 0.54 mg / mL, 0.84 mg / mL, 1.18 mg / mL, 1.57 mg / mL and 2.45 mg / mL respectively, wherein the concentration of the internal standard is 10.02 mg / mL.
[0035] Formula I: , wherein W i is the mass of the substance i to be measured in the standard solution, g; W s is the mass of the internal standard in the standard solution, g; A i is the peak area of the substance i to be measured in the standard solution; A s is the peak area of the internal standard in the standard solution; the substance i to be measured is tert-butyl hydroperoxide, di-tert-butyl hydroperoxide or tert-butyl alcohol.
[0036] The standard solution of tert-butyl hydroperoxide with different concentrations was detected by gas chromatography, the relative correction factor of the standard solution of tert-butyl hydroperoxide was calculated according to Formula I, and the standard curve of the relative correction factor of tert-butyl hydroperoxide was drawn with the mass ratio of tert-butyl hydroperoxide to the internal standard as the abscissa and the peak area ratio of tert-butyl hydroperoxide to the internal standard as the ordinate, as shown in Figure 1 . The linear equation of the standard curve of the relative correction factor of tert-butyl hydroperoxide is y = 17.606x + 0.0069, R 2 = 0.9999.
[0037] The standard solution of di-tert-butyl hydroperoxide with different concentrations was detected by gas chromatography, the relative correction factor of the standard solution of di-tert-butyl hydroperoxide was calculated according to Formula I, and the standard curve of the relative correction factor of di-tert-butyl hydroperoxide was drawn with the mass ratio of di-tert-butyl hydroperoxide to the internal standard as the abscissa and the peak area ratio of di-tert-butyl hydroperoxide to the internal standard as the ordinate, as shown in Figure 2 . The linear equation of the standard curve of the relative correction factor of di-tert-butyl hydroperoxide is y = 22.213x + 0.0054, R 2 = 0.9989.
[0038] The standard solution of tert-butyl alcohol with different concentrations was detected by gas chromatography, the relative correction factor of the standard solution of tert-butyl alcohol was calculated according to Formula I, and the standard curve of the relative correction factor of tert-butyl alcohol was drawn with the mass ratio of tert-butyl alcohol to the internal standard as the abscissa and the peak area ratio of tert-butyl alcohol to the internal standard as the ordinate, as shown in Figure 3 . The linear equation of the standard curve of the relative correction factor of tert-butyl alcohol is y = 23.317x + 0.0095, R 2 = 0.9995.
[0039] Equation II: wherein, C i is the mass content of the measured substance i in the t-butyl hydroperoxide synthesis reaction solution; W s is the mass of the internal standard in the t-butyl hydroperoxide synthesis reaction solution, g; W is the mass of the t-butyl hydroperoxide synthesis reaction solution, g; A i is the peak area of the measured substance i in the t-butyl hydroperoxide synthesis reaction solution; A s is the peak area of the internal standard in the t-butyl hydroperoxide synthesis reaction solution; k i is the relative correction factor of the measured substance i; the measured substance i is t-butyl hydroperoxide, di-t-butyl hydroperoxide or t-butyl alcohol.
[0040] Take 0.34 g of t-butyl hydroperoxide synthesis reaction solution and place it in a 10 mL volumetric flask, add 2 mL of internal standard solution, and then use methanol to make up the volume and shake well. Perform gas chromatography detection, and calculate the content of t-butyl hydroperoxide, di-t-butyl hydroperoxide and t-butyl alcohol in the t-butyl hydroperoxide synthesis reaction solution according to Equation II. Figure 4 is the gas chromatogram of the t-butyl hydroperoxide synthesis reaction solution. The calculation result is that the mass content of t-butyl hydroperoxide in the t-butyl hydroperoxide synthesis reaction solution is 80.992%, the mass content of the byproduct di-t-butyl hydroperoxide is 3.705%, and the mass content of the unreacted raw material t-butyl alcohol is 1.139%.
[0041] Example 2
[0042] Quantitative analysis of continuous t-butyl hydroperoxide synthesis reaction solution, Figure 5 is a flow diagram of the continuous t-butyl hydroperoxide synthesis reaction. Sulfuric acid (mass fraction of 98%) and hydrogen peroxide solution (mass fraction of 50%) are mixed to continuously prepare an acidic hydrogen peroxide solution (blue area); the t-butyl alcohol solution mixed with the internal standard (mass fraction of t-butyl alcohol is 95%, and the mass of the internal standard is 2% of the mass of t-butyl alcohol) is preheated and mixed with the acidic hydrogen peroxide solution to perform a synthesis reaction (red area). The temperature for continuously preparing the acidic hydrogen peroxide solution is 25°C, the feeding flow rate of sulfuric acid is 0.559 mL / min, the feeding flow rate of hydrogen peroxide solution is 2.332 mL / min, and the residence time for mixing sulfuric acid and hydrogen peroxide solution is 3.5 min; the temperature for the synthesis reaction is 40°C, the preheating time for the t-butyl alcohol solution mixed with the internal standard is 3 min, and the feeding flow rate is 2.109 mL / min. After the synthesis reaction starts, the synthesis reaction solution at different times is analyzed by gas chromatography, the content of t-butyl hydroperoxide, di-t-butyl hydroperoxide and t-butyl alcohol in the continuous t-butyl hydroperoxide synthesis reaction solution is calculated according to Equation II, and then the conversion rate of t-butyl alcohol and the selectivity of t-butyl hydroperoxide are calculated. The results are shown in Table 1.
[0043] Table 1 Raw material conversion rate and product selectivity in continuous tert-butyl hydroperoxide synthesis reaction process
[0044] Example 3
[0045] The standard addition recovery rate of each component was verified, and the results are shown in Tables 2-4.
[0046] Table 2 Standard addition recovery rate of tert-butyl alcohol TBA
[0047] Table 3 Standard addition recovery rate of tert-butyl hydroperoxide
[0048] Table 4 Standard addition recovery rate of di-tert-butyl hydroperoxide
[0049] As can be seen from Tables 2-4, the standard addition recovery rate of each component in the quantitative analysis method of the application is between 89.4-106.7%.
[0050] Example 4
[0051] Repeatability verification
[0052] A mixed standard solution mixed with an internal standard 2-hexanol was prepared, and the concentration of tert-butyl hydroperoxide in the mixed standard solution was 28.846 mg / mL, the concentration of tert-butyl alcohol was 2.0642 mg / mL, the concentration of di-tert-butyl hydroperoxide was 4.0934 mg / mL, and the concentration of the internal standard 2-hexanol was 10.019 mg / mL. The mixed standard solution was repeatedly detected by gas chromatography for 6 times to verify the standard deviation of each component of the quantitative analysis method of the application. Figure 9 The gas chromatogram of the first time gas chromatography detection of the mixed standard solution mixed with the internal standard 2-hexanol. The standard deviation of each component is shown in Tables 5-7.
[0053] Table 5 Standard deviation of tert-butyl hydroperoxide TBHP
[0054] Table 6 Standard deviation of di-tert-butyl hydroperoxide DTBP
[0055] Table 7 Standard deviation of tert-butyl alcohol TBA
[0056] As can be seen from Tables 5-7, the quantitative analysis method of the present application has high repeatability.
[0057] Comparative Example 1
[0058] The difference from Example 1 is that the internal standard 2-hexanol is replaced by ethyl acetate.
[0059] Figure 10 The gas chromatogram of the tert-butyl hydroperoxide standard solution in Comparative Example 1 is shown in Figure 1. Figure 10 As can be seen, the retention time of ethyl acetate is 5.318 min, which is very close to the retention time (4.547 min) of the raw material tert-butanol, and is easy to affect the peak area results of tert-butanol in the synthetic reaction liquid. The retention time of the internal standard 2-hexanol in the present application is 14.299 min, which is far apart from the characteristic peaks of tert-butanol, di-tert-butyl hydroperoxide and tert-butyl hydroperoxide, and has no effect on the peak areas of tert-butanol, di-tert-butyl hydroperoxide and tert-butyl hydroperoxide.
[0060] As can be seen from the above examples, the present application provides a quantitative analysis method for the synthetic reaction liquid of tert-butyl hydroperoxide, uses 2-hexanol as an internal standard, and uses gas chromatography for quantitative analysis. Under the same detection conditions, the contents of the main product tert-butyl hydroperoxide, the by-product di-tert-butyl hydroperoxide and the unreacted raw material tert-butanol in the synthetic reaction liquid can be obtained, which has high precision and good repeatability, and the accuracy is higher than that of the detection result using ethyl acetate as an internal standard.
[0061] The above description is only the preferred embodiments of the present application, and it should be pointed out that for ordinary skilled in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should be considered as the protection scope of the present application.
Claims
1. A quantitative analysis method for the reaction solution in the synthesis of tert-butyl hydrogen peroxide, characterized in that, It includes the following steps: 1) Place the internal standard 2-hexanol in a volumetric flask and dilute to volume with methanol to obtain the internal standard solution; 2) Mix the tert-butyl hydrogen peroxide synthesis reaction solution and the internal standard solution, and perform gas chromatography detection. Based on the peak area and the standard curve of the relative correction factor, calculate the contents of tert-butyl hydrogen peroxide, tert-butanol and di-tert-butyl hydrogen peroxide in the tert-butyl hydrogen peroxide synthesis reaction solution.
2. The quantitative analysis method according to claim 1, characterized in that, The relative correction factor standard curves include the relative correction factor standard curves for tert-butyl hydroperoxide, tert-butanol, and di-tert-butyl hydroperoxide.
3. The quantitative analysis method according to claim 2, characterized in that, The method for plotting the standard curve of the relative correction factor of tert-butyl hydroperoxide includes the following steps: ① Place different masses of tert-butyl hydrogen peroxide standard into volumetric flasks, add internal standard solution, and dilute to volume with methanol to obtain tert-butyl hydrogen peroxide standard solutions of different concentrations. ② Gas chromatography was used to detect tert-butyl hydrogen peroxide standard solutions of different concentrations. The relative correction factor standard curve of tert-butyl hydrogen peroxide was plotted with the mass ratio of tert-butyl hydrogen peroxide to internal standard as the abscissa and the peak area ratio of tert-butyl hydrogen peroxide to internal standard as the ordinate.
4. The quantitative analysis method according to claim 3, characterized in that, The method for plotting the standard curve of the relative correction factor of tert-butanol includes the following steps: a) Place different masses of tert-butanol standards into volumetric flasks, add internal standard solution, and dilute to volume with methanol to obtain tert-butanol standard solutions of different concentrations. b) Gas chromatography was used to detect tert-butanol standard solutions of different concentrations. The relative correction factor standard curve of tert-butanol was plotted with the mass ratio of tert-butanol to internal standard as the abscissa and the peak area ratio of tert-butanol to internal standard as the ordinate.
5. The quantitative analysis method according to claim 4, characterized in that, The method for plotting the standard curve of the relative correction factor of di-tert-butyl hydroperoxide includes the following steps: A) Different masses of di-tert-butyl hydrogen peroxide standard were placed in volumetric flasks, internal standard solution was added, and the volume was adjusted with methanol to obtain di-tert-butyl hydrogen peroxide standard solutions of different concentrations. B) Gas chromatography was used to detect di-tert-butyl peroxide standard solutions of different concentrations. The relative correction factor standard curve of di-tert-butyl peroxide was plotted with the mass ratio of di-tert-butyl peroxide to internal standard as the abscissa and the peak area ratio of di-tert-butyl peroxide to internal standard as the ordinate.
6. The quantitative analysis method according to any one of claims 1 to 5, characterized in that, The detector used for gas chromatography detection is an FID detector, and the chromatographic conditions for gas chromatography detection are as follows: Chromatographic column: DB-1701, 30m × 0.32mm × 0.25μm Carrier gas flow rate: 0.5~1.5 mL / min Vaporization chamber temperature: 100~120℃ Detector temperature: 220~240℃ Flow split ratio: 43~47:1 Injection volume: 0.5~1.5μL Column oven temperature: 35~45℃, hold for 10 minutes Heating rate: 8~12℃ / min, heating up to 140℃.