Thermal Hazard Evaluation of Cumene Hydroperoxide (CHP) Using Isothermal and Heating Method

Thermal Hazard Evaluation of Cumene Hydroperoxide (CHP) Using Isothermal and Heating Method Sheng-Hung Wu*1, Pao-Wen G. Liu2, Ying-Ting Lin3, Chiao-Li Shih4, Tung-Tin Wu5 Department of Tourism and Hospitality, TransWorld University, 1221, Zhennan Rd., Douliou, Yunlin 640, Taiwan, ROC 1,4

Deparment of Safety Health and Environmental Engineering, Chung Hwa University of Medical Technology, Tainan, Taiwan, ROC 2,3

Green Carbon Science Technology Co., Ltd., Kaohsiung, Taiwan, ROC

5

wushprofessor@gmail.com; 2graceliu@mail.hwai.edu.tw

*1

Abstract Cumene hydroperoxide (CHP) is a explosive chemical in the chemical industry in Taiwan that can be identified as organic peroxide (OP). Therefore, CHP can be manufactured using cumene mixed with oxygen or air (21% O2) in the oxidation tower and can be an important chemical and hazardous chemical for dicumyl peroxide (DCPO) process, acrylonitrile-butadienestyrene (ABS) process, and phenol and acetone manufacturing plant. Since 1981-2010 in Taiwan, plenty of thermal explosion accidents of CHP were recorded and analyzed in Taiwan. Therefore, this study was applied to analyze thermal hazard of CHP using an isothermal calorimeter. The reaction order (n) was calculated to be 0.5 that can be used to simulate a thermal explosion accident and to determine thermokinetics in the CHP oxidation process. This study was applied to analyze thermal hazard of CHP in the oxidation tower using the differential scanning calorimetry (DSC) with isothermal and heating method. The temperature of an exothermic reaction of 30, 80, and 88 mass % CHP can be analyzed less than 90℃ in the oxidation tower. The critical temperature of 30, 80, and 88 mass% CHP can be evaluated less than 100℃.

Keywords Cumene Hydroperoxide (CHP); Organic Peroxide (OP); Acrylonitrile-butadiene-styrene (ABS); Reaction Order (n); Exothermic Reaction

Introduction Benzene and propylene are used to produce cumene in the traditional process in Taiwan. Therefore, cumene mixed with air or oxygen in six oxidation towers has been employed to yield various cumene hydroperoxide (CHP) concentrations in the chemical industries [1]. Cumene is a reactant and can be oxidized to produce CHP at temperature in the 80–120°C and at a pressure ranging from atmospheric to 700 kPa [1].

The first oxidation tower can be applied to produce 20–30 mass% CHP using two flow process. Therefore, 60 mass% CHP can be concentrated in second oxidation tower. Finally, 80% CHP is concentrated in third oxidation tower that can be used as the initiator of acrylonitrile-butadiene-styrene (ABS) process in Taiwan [2].

During 1981-2010 in Taiwan, CHP has caused eight accidents including oxidation tower, reactor, storage tank, and transportation. Especially, thermal explosion of CHP in the oxidation tower in 2010 in Taiwan has occurred and was investigated. This study was applied to analyze thermal hazard of CHP in the oxidation and to evaluate the potential hazard during the operation [3–7].

This study was applied to analyze thermal hazard of CHP in the oxidation tower using the differential scanning calorimetry (DSC) with isothermal and heating method. The temperature of an exothermic reaction of 30, 80, and 88 mass % CHP can be analyzed less than 90℃ in the oxidation tower. The critical temperature of 30, 80, and 88 mass% CHP can be evaluated less than 100℃.

International Journal of Engineering Practical Research, Vol. 4 No. 1-April 2015 2326-5914/15/01 103-04 © 2015 DEStech Publications, Inc. doi: 10.12783/ijepr.2015.0401.20

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Sheng-Hung Wu, Pao-Wen G. Liu, Ying-Ting Lin, Chiao-Li Shih, Tung-Tin Wu

Experiment First, DSC was applied to test thermal behavior under various isothermal temperature including 90–130℃ holding 10 hrs and to analyze thermal decomposition behaviors of 30, 80, and 88 mass% CHP by isothermal model of DSC. Second, the same crucible after isothermal temperature holding 10 hrs was used to evaluate the thermal hazard of 30, 80, and 88 mass% CHP under 4℃ min–1 of heating rate (from 30 to 300℃).

Results and Discussion To calculate the T0, this study was applied to develop a new method for the T0 determination. First, this study was applied to teat thermal decomposition behavior 30 mass% CHP by using isothermal model of DSC under 90–130℃ holding 10 hrs and non-isothermal situation. Second, we did not take out the crucible of the sample and do the experiment under 4℃ min–1 of heating rate by DSC. The aim of this test was to analyze if the material was catalyzed to decompose. Thirty mass% CHP was analyzed in Figure 1 The T0 of 30 mass% CHP can be analyzed less than 90℃. According to Figure 1, the peak of non-isothermal test is higher than the experiment under 90℃ of isothermal test. Therefore, the T0 of 30, 80, 90 mass% CHP under non-isothermal condition by DSC was identified less than 90℃. In fact, the environmental temperature at 90℃ can catalyze the CHP decomposition. The ΔHd of 30 mass% CHP under non-isothermal situation was determined to be 545 W g–1. The ΔHd of 30 mass% CHP under 90℃ holding 10 hrs was determined to be 462 W g–1. Therefore, 90℃ can catalyze the 30 mass% CHP to decompose in the oxidation tower or reactor. Therefore, the T0 was identified less than 80℃. Eighty and 88 mass% CHP was analyzed in Figures 2 to 3. According to Figure 2, the ΔHd of 80 mass% CHP for a non-isothermal test is higher than the experiment under 90°C of isothermal test. Eighty-eight mass% was used to test using the same method.

The ΔHd of 88 mass% CHP was determined to be 1,200 J g–1. The ΔHd of 88 mass% CHP under 90℃ holding 10 hrs was determined to be 1,100 J g–1.

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Temperature ( C) FIGURE 1. THERMAL BEHAVIOU DETERMINATION OF 30 MASS% CHP BY DSC USING ISOTHERMAL-HEATING METHOD.

Conclusions The reaction order (n) can be analyzed to be 0.5. Thermal hazard of CHP in the oxidation tower using the differential scanning calorimetry (DSC) with isothermal and heating method can be applied to determine the temperature of an exothermic reaction in the CHP manufacturing process.The temperature of an exothermic reaction of 30, 80, and 88 mass% CHP can be analyzed less than 90℃ in the oxidation tower. The critical temperature of 30, 80, and 88 mass% CHP can be evaluated less than 100℃.

Thermal Hazard Evaluation of Cumene Hydroperoxide (CHP) Using Isothermal and Heating Method

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Temperature ( C) FIGURE 2. THERMAL BEHACIOR DETERMINATION OF 80 MASS% CHP BY DSC USING ISOTHERMAL-HEATING METHOD.

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Temperature ( C) FIGURE 3. THERMAL BEHAVIOR DETERMINATION OF 88 MASS% CHP BY DSC USING ISOTHERMAL-HEATING METHOD. REFERENCES

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