Smart Technology for Evaluating Fire Extinguishing Effect of tert-Butyl Hydroperoxide

Smart Technology for Evaluating Fire Extinguishing Effect of Tert-butyl hydroperoxide

Kuo-Yi Li,

Department of Industrial Engineering and Management, National Chin-Yi University of Technology, 57, Sec. 2, Zhongshan Rd., Taiping Dist., Taichung, Taiwan 41170, ROC

Shu-Yao Tsai, Chun-Ping Lin*,

Department of Health and Nutrition Biotechnology, College of Health Science, Asia University, 500, Lioufeng Rd., Wufeng, Taichung, Taiwan 41354, ROC

Yun-Ting Tsai, Chi-Min Shu

Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science

and Technology, 123,University Rd., Sec. 3, Douliou, Yunlin, Taiwan 64002, ROC

*To whom correspondence should be addressed. Fax: +886-4-2332-1126.

E-mail: cp.lin@asia.edu.tw

Abstract

Tert-butyl hydroperoxide (TBHP) 70 mass%, a solution of liquid peroxide, has been widely

employed in the chemical industry as a polymerization initiator. The smart technology for predicting

the mechanism of thermal decomposition and the inhibitive or hazardous reaction of TBHP by

different calorimetric tests involves using differential scanning calorimetry (DSC) non-isothermal

tests versus DSC isothermal tests and vent sizing package 2 (VSP2) adiabatic tests versus DSC non-

isothermal tests, respectively, for further understanding how to extinguish organic peroxide accidents

under fire scenario or runaway reaction in a chemical plant. Meanwhile, TBHP mixed with inhibitive

and hazardous materials, such as various protic acids to help prevent runaway reactions, was applied

on fires or explosions in the fire system. The results could be available to fire-related agencies as a

reference application. The fire extinguishing system must be well designed for decreasing the degree

of hazard.

1. Introduction

Tert-butyl hydroperoxide (TBHP) is a solution of liquid organic peroxide that has been widely employed in the chemical industry and used to manufacture polymer materials. It is a commercial liquid organic peroxide which needs to be stored under limited temperature. In terms of manufacturing and storage management, many serious explosions and high ambient temperature have occurred from its thermal decomposition and incompatible reaction.

Organic peroxides have caused many serious accidents including fire extinguishing accidents, tank storage, and transportation. One reason for accidents involves the peroxy group (–O–O–) of organic peroxides, due to its thermal instability and high sensitivity to thermal sources or ambient temperature.

Table 1 shows the selected thermal explosion accidents caused by organic peroxides in Asia

, and the thermal runaway reaction and explosion accidents of organic peroxides in chemical plant in Taiwan are displayed in Figure 1.

In particular, organic peroxides cannot be mixed with incompatible materials, such as strong acid strong base and special metal powder, which are used for fire extinguishing the organic peroxides in the chemical plant. Actually, suitable fire-fighting equipment can be applied to reduce losses and protect life and property. The fire extinguishing agent of monoammonium phosphate has been used in the current fire extinguishing system.

This study focused on the organic peroxide mixed with phosphoric acid or the other protic acids, such as sulfuric acid and nitric acid, which can be used for understanding inhibitive and hazardous reactions of organic peroxides under thermal decompositions, and which also could be used to optimize the fire extinguishing system to decrease the degree of hazard of organic peroxide accidents.

TBHP is also very sensitive to heat due to the unstable structure of the peroxy group. If temperature is not well controlled, the system becomes unstable and eventually triggers a runaway reaction in the next stage, potentially leading to various types of accidents.

Organic peroxides have complex decomposition characteristics, and we still lack detailed information about them, especially during the runaway reactions. This aim of this study on TBHP is on inhibitive and hazardous reactions of mixing with various protic acids, and on evaluating the thermal hazard and discussing the phenomenon of runaway reactions.

First, we could achieve our aim through a novel and effective thermal analysis technology, a

special method. Via simple differential scanning calorimetry (DSC) tests and kinetics predictions, the

thermal hazard properties of organic peroxides can be evaluated. Comparisons of swift non-

isothermal and isothermal-kinetic model simulations led to a reliable mechanism of thermal

decomposition to predict the parameters of TBHP.

The selected approach was to establish an

effective model for thermal decomposition that included the kinetic parameters and thermal hazard

properties,

such as the activation energy (E

), frequency factor (lnk

), heat of decomposition (∆H

), and reaction order (n), of TBHP.

Secondly, we considered the scenarios when various protic acids are mixed, e.g., monoprotic acid (HNO

), diprotic acid (H

SO

), and triprotic acid (H

PO

), respectively, to predict the inhibitive and hazardous materials in TBHP’s thermal stability. The reaction equations of protic acids from Eqs. (1) to (3) are as follows:

Monoprotic acid

HNO

+ H

O ⇌ H

O

+ NO

(1) Diprotic acid

H

SO

+ H

O ⇌ H

O

+ HSO

HSO

+ H

O ⇌ H

O

+ SO

(2) Triprotic acid

H

PO

+ H

O ⇌ H

O

+ H

PO

H

PO

+ H

O ⇌ H

O

+ HPO

HPO

+ H

O ⇌ H

O

+ PO

(3)

Following the above-mentioned reactions for the prediction results of the original sample of TBHP, we then compared the DSC non-isothermal and the vent sizing package 2 (VSP2) adiabatic- kinetic model simulations to predict the runaway reaction, the inhibitive reaction, and the hazardous reaction of TBHP mixed with various protic acids.

Kinetic model simulation was employed to construct a novel and effective procedure to evaluate the safety parameters for the inhibitive and hazardous reaction of TBHP. The chosen approach could establish a smart technology for thermal decomposition properties that includes the kinetics and hazardous reaction for TBHP, and when mixed with inhibitive or hazardous materials, respectively.

The approach applies the optimal conditions to avoid TBHP’s violent runaway reactions during process manufacturing and storage.

Ultimately, this study’s results could be available to fire-related agencies as a reference application. However, in earlier studies the thermal hazard analysis method was rarely employed to assess and calculate the inhibitive and hazardous reaction for TBHP mixed with various protic acids.

The fire extinguishing system must be well designed for decreasing the degree of hazard. Disaster can be prevented in the first stage, and the results of this study are expected to aid process safety for preventing an accident from occurring.

2. Kinetic simulation

Simulations of kinetic models can be complex multi-stage reactions that may consist of several independent, parallel, and consecutive stages, demonstrated as described by the following equations.

8–12

The initial conditions are as follows:

1 1 1 ( ) 1

d r k T f

dt

 _{ }

(4)

2 1 2 ; 2 2 ( ) 2

d r r r k T f

dt

 _{  }

(5)

3 2 3 ; 3 3 ( ) 3

d r r r k T f

dt

 _{  }

(6)

4 3

d r

dt

 _

(7)

0; _i 0; 1, 2, 3, 4

t    i 

where α

, α

, α

, and α

are the degrees of conversion of a reaction or stage, r

, r

, and r

are reaction rates of a reaction or stage, k

, k

, and k

are the rate constants of a reaction or stage, and f

, f

, and f

are the kinetic functions of a reaction or stage.

Simple one-step reaction: AB:

0

 

Ea

d k e

f dt

 



 (8)

  ^{(1 )}

f     n-th order (9)

  ^{(1 ) (}

⁾

f       z autocatalytic (10)

where E

is the activation energy, k

is the pre-exponential factor, z is the autocatalytic constant, n

and n

are reaction orders of the specific stage.

Reaction including two consecutive stages: ABC:

1 2

1 2

1

(1 ) ;

( )

E E

n n

RT RT

d d

k e k e

dt dt

    

 

   

(11)

where  and  are the conversions of the reactant A and product C, respectively, and E

and E

are activation energies of stage one and two, respectively.

Two-parallel equations are a useful model of full autocatalysis:

1 2 3

1 1

1 2

2 2

( ) ( )(1 ) ( ) ( );

( ) ( ) (1 )

n n n

r k T

d r r

dt r k T

 

  

  

 

 

  (12)

where k

and k

are rate constants of a specific reaction or stage, n

is the reaction order of stage three.

3. Experimental and method 3.1.Samples

TBHP 70 mass% solution, which was supplied directly from ACE Chemical Corp in Taiwan, was stored in a refrigerator at 4 °C. Experiments involving DSC non-isothermal tests were conducted at various scanning rates of 1 and 2 °C/min. DSC isothermal tests were held at 125 and 130 °C for TBHP. The original TBHP 15 mass% 20 mL, the TBHP 15 mass% mixed in 4 mL 6N HNO

, the TBHP 15 mass% mixed in 4 mL 6N H

SO

and, the TBHP 15 mass% mixed in 4 mL 6N H

PO

were analyzed, respectively by VSP2 adiabatic runaway reaction tests. In addition, to avoid bursting the test cell and losing all of the exothermic data, the VSP2 tests only served with 10–25 mass%.

3.2.Differential scanning calorimetry (DSC)

Temperature–programmed screening experiments were performed with DSC (TA Q20). The test cell was used to carry out the experiment for withstanding relatively high pressure to approximately 10 MPa. ASTM E698 was used to obtain thermal curves for calculating kinetic parameters. Approximately 2–3 mg of the sample was used to acquire the experimental data of non- isothermal tests and isothermal tests. We used nitrogen as the carrier gas, which flow rate was 15 mL/min. Non-isothermal tests of the scanning rate selected for the programmed temperature ramp were 1, 2, 4, and 8 °C/min. The range of temperature rise chosen was from 30–300 °C for each experiment. Isothermal tests of the held isothermal condition were several at 125, 130, 135, and 140

°C. The results for the thermal decompositions of TBHP from the non-isothermal and isothermal of DSC tests are listed in Table 2, and the test curves of DSC are in Figures 2 and 3, respectively.

In addition, non-isothermal hazardous reaction tests were conducted with the scanning rate 4

°C/min; about 6–7 mg of the sample was used to acquire the experimental data, and the range of

temperature rise chosen was from 30–300 °C for each experiment. The results for the thermal

decompositions of TBHP from the DSC non-isothermal hazardous reaction tests are in Table 3, and

the test curves of DSC are in Figure 4.

3.3.Vent sizing package 2 (VSP2)

VSP2, developed by Fauske and Associates, Inc., is a highly sensitive calorimeter that can obtain thermokinetic and thermal decomposition data, such as temperature and pressure traces with respect to time in an adiabatic calorimeter system by PC-control. Under heating conditions, the main heater will heat the sample to a pre-set temperature, and then a guard heater turns on to maintain an adiabatic surrounding.

In the experimental conditions, if the self-heating rate is larger than 0.02

°C/min the heat-wait-search stage and main heater should be immediately stopped for measuring the original phenomenon of self-exothermicity.

To adequately protect the normal operation of this apparatus and avoid bursting the test cell and losing the end of exothermic data, 15 mass% 20 mL, mixed in 4 mL 6N HNO

, mixed in 4 mL 6N H

SO

, and mixed in 4 mL 6N H

PO

of TBHP were prudently prepared for the experiments. Thermokinetic and pressure behavior in the same test cell (112 mL) usually could be tested without any difficult extrapolation to the process scale due to a low thermal inertia factor (Φ) of about 1.05 to 1.32. Here, the 1.1 of thermal inertia factor (Φ) was applied to evaluate the runaway reaction and to simulate the kinetic parameters in this study. The results for the adiabatic runaway reaction of the TBHP’s 15 mass%, mixed in 6N HNO

, mixed in 6N H

SO

, and mixed in 6N H

PO

of VSP2 tests are in Table 4. The temperature versus time and the pressure versus time are in Figures 5 and 6.

4. Results and discussion

4.1.Evaluation of TBHP mechanism of thermal decomposition by DSC

The kinetic parameters were determined from the DSC experimental data at various scanning rates of 1, 2, 4, and 8 °C/min and isothermal tests holding isothermal conditions of 125, 130, 135, and 140 °C for TBHP. The thermal decomposition of TBHP represents an unknown reaction mechanism, such as an n-th order or autocatalytic reaction. Comparisons of the TBHP’s DSC non- isothermal and isothermal tests of the experimental data and data derived from simulated n-th order reaction and autocatalytic reaction, respectively, from Tables 5 and 6 show the results match very well those of the autocatalytic simulations for TBHP by simple non-isothermal and isothermal- kinetic-model simulation, respectively. This is in contrast to the fact that the TBHP use of simulated autocatalytic kinetic models to match original DSC experimental data, respectively, was proven to give superior results.

Moreover, a comparison of Tables 2, 5, and 6 shows the samples were tested under isothermal

conditions; to compare, the overheating effect was greater than non-isothermal DSC tests. The result

was explicit: the DSC isothermal tests simulation was not appropriately applied on TBHP’s kinetic

evaluation in this study. The outcomes of DSC isothermal-kinetic-model simulation were concerned with the overheating effect of the kinetic parameters for TBHP. Fortunately, the comparisons of the kinetics of non-isothermal and isothermal-kinetic-model simulation, TBHP’s kinetic parameters, indicate that the mechanism of thermal decomposition belongs to an autocatalytic reaction in this study.

4.2.Prediction of TBHP inhibitive and hazardous reaction by DSC and VSP2

Table 3 shows the results of the inhibitive and hazardous reactions of TBHP mixed with various protic acids by DSC non-isothermal tests. In contrast to Tables 2 and 3, for the TBPB mixed in 6N HNO

, the heat of decomposition was greater than the other polyprotic acids, which was also more than the original samples of TBHP (see Table 2). Thus, from the result of inhibitive and hazardous reaction of non-isothermal tests, we could observe the mixing with 6N HNO

in TBHP, which causes a hazardous reaction for TBHP.

Figure 5 shows the temperature versus time for thermal decomposition of TBHP’s 15 mass%, mixed in 6N HNO

, mixed in 6N H

SO

, and mixed in 6N H

PO

by VSP2. The pressures versus time by VSP2 under of 15 mass% and mixed in various protic acids is shown in Figure 6. For mixing in 6N H

SO

, as in Figure 4, T

reached 286.5 °C and Figure 6, for mixing in 6N HNO

, P

reached 42.6 bar, which was greater than the other polyprotic acids. Respectively, the (dT/dt)

and (dP/dt)

of mixing in 6N HNO

were about 3448.3 °C/min and 2469.5 bar/min (Table 4). The critical point for the chemical explosion under constant volume reactor immediately reaches the maximum pressure, which is a very dangerous condition for process manufacturing or storage.

Accordingly, the kinetics of TBHP’s thermal decomposition was predicted from autocatalytic reaction simulation. Tables 7 and 8 present the results of the non-isothermal and adiabatic-kinetic- model autocatalytic simulation, respectively. From Table 7, in contrast to the fact that the use of simulated autocatalytic kinetic models to match the thermal decomposition properties of original DSC experimental data was proven to give superior results, the results were compatible with the model. In addition, from Tables 7 and 8, we also observed that the E

values, the TBHP mixed in 6N HNO

were smaller than the mixing in other polyprotic acids, which were providing remarkable results for mixing with 6N HNO

in TBHP and was an incompatible reaction too. The reason was that that the incompatible material destroyed the thermal stability of TBHP.

From prediction of the incompatible reaction of TBHP mixed with various protic acids, the

TMR

, TER, and TCL were acquired by simulating autocatalytic non-isothermal kinetics, as in

Figures 7–9. However, we used a low concentration of TBHP solution as 15 mass% for VSP2 tests,

which cannot represent the original sample in this study. Thus, from the result of adiabatic kinetic

simulation, the data set was also excluded from further analysis.

Here, in contrast to Figures 7–9, the use of simulated autocatalytic kinetic models was proven to give superior results. Figure 7 shows the TMR

of TBHP and mixed in 6N H

PO

were obtained, which values were less than 34.55 °C and exceeded the upper limit of 100 days; but mixed in 6N HNO

were less than 20 °C and exceeded the upper limit of only 1.9 days. Especially, Figure 8 shows the TER of TBHP mixed in HNO

and H

SO

immediately reaches the maximum energy release. Figure 9 shows the TCL of TBHP and mixed in 6N H

PO

are less than 20 °C, which is beyond the upper limit of 10 years, but TBHP mixed in 6N HNO

is very unstable, which is beyond the upper limit of only 9.23 days. In addition, from the prediction of TBHP’s incompatible reactions, which showed noticeable results of TBHP mixed in triprotic acid-H

PO

could be successfully inhibiting the runaway reaction, but TBHP mixed in monoprotic acid-HNO

destroyed the thermal stability, along with enhancing the exothermic effect.

We have developed a method using the DSC data and then validated the results using the VSP2 experimental data to determine the kinetics and the inhibitive reaction and hazardous reaction of TBHP. These results could be applied toward energy reduction and safer designs for a fire extinguishing system. In addition to through effective DSC analysis technology and accurate VSP2 runaway reaction assessment, we found that the results presented a reasonable thermal hazard assessment method for preventing runaway reactions, fires or explosions. This method can also be used to assess and calculate the inhibitive and hazardous reaction for the other organic peroxides mixed with incompatible materials.

5. Conclusions

This study has exhibited an effective technology to predict reliable kinetics and parameters that can precisely and effectively predict the hazardous reaction of TBHP. The results showed that TBHP mixed in H

PO

could inhibit a runaway reaction by heat effect, but TBHP mixed in HNO

destroyed the thermal stability, along with enhancing the exothermic effect.

The use of various calorimetric tests can avoid the inaccuracy of a single thermal analysis method or mono-calorimetric test. Kinetic model simulation was employed to construct a novel and effective procedure to evaluate the safety model for the inhibitive and hazardous reaction of organic peroxides. The approach also applies the optimal conditions to avoid organic peroxides’ violent runaway reactions during fire system, process manufacturing, and storage.

Therefore, the results from this study could be available to fire-related agencies as a reference application. The fire extinguishing system must be well designed for decreasing the degree of hazard.

Disaster can be prevented in the earlier stage, and the results of this study are expected to aid process

safety for preventing an accident from occurring.

Acknowledgments

The authors are indebted to the donors of National Science Council (NSC), Taiwan, R.O.C.

under the contract No.: NSC 100-2218-E-468-001- for financial support. In addition, we are grateful to Prof. Jo-Ming Tseng for technical support on the DSC experiments and ACE Chemical Corp. in Taiwan for providing the TBHP.

Nomenclature

E

activation energy (kJ/mol)

E

activation energy of the 1st stage (kJ/mol) E

activation energy of the 2nd stage (kJ/mol) f

kinetic functions of the i-th stage; i = 1, 2, 3 f(α) kinetic functions

k

pre-exponential factor (M

/sec) k

reaction rate constant (1/sec); i = 1, 2

n

reaction order of the i-th stage, dimensionless; i = 1, 2, 3 P

maximum explosion pressure (bar)

r

reaction rate of the i-th stage (g/sec); i = 1, 2, 3, 4 T absolute temperature (K)

TCL time to conversion limit (day) TER total energy release (kJ/kg)

T

maximum explosion pressure (°C)

TMR

time to maximum rate under isothermal conditions (day) T

peak temperature (°C)

t time (sec)

z autocatalytic constant, dimensionless

(dP/dt)

maximum rate of explosion pressure rise (bar/min) (dT/dt)

maximum rate of explosion temperature rise (°C/min)

Greek letters

α degree of conversion, dimensionless

α

degree of conversion of the i-th stage, dimensionless; i = 1, 2, 3, 4

γ degree of conversion, dimensionless

r

reaction rate of 1st stage (g/sec) r

reaction rate of 2nd stage (g/sec)

∆H

heat of decomposition (kJ/kg)

Φ thermal inertia factor, dimensionless

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Table captions

Table 1. Selected Thermal Explosion Accidents Caused by Organic Peroxides in Asia

Table 2. Results of Various DSC Tests of TBHP with Scanning Rates of 1, 2, 4, and 8 °C/min and under Different Isothermal Conditions of 125, 130, 135, and 140 °C

Table 3. Results of Hazardous Reaction of TBHP Mixed with Various Protic Acids by DSC Non- isothermal tests

Table 4. Results of Thermal Runaway Reaction of TBHP and Mixed with Various Protic Acids by VSP2 Tests

Table 5. Comparisons of TBHP’s Kinetic Parameters for the Evaluation of N-th Order and Autocatalytic Models under Non-isothermal Condition

Table 6. Comparisons of TBHP’s Kinetic Parameters for the Evaluation of N-th Order and Autocatalytic Models under Isothermal Condition

Table 7. The Kinetic Parameters Evaluated TBHP Mixed with Various Protic Acids by Non- isothermal Autocatalytic Model Simulation

Table 8. The Kinetic Parameters Evaluated TBHP and Mixed with Various Protic Acids by

Adiabatic Autocatalytic Model Simulation

Table 1.

Selected Thermal Explosion Accidents Caused by Organic Peroxides in Asia

date location hazardous injuries fatalities units

1953 Tokyo explosion 3 0 N/A

1953 Hyougo explosion 1 0 N/A

1958 Tokyo explosion 0 0 N/A

1958 Aichi explosion 1 0 N/A

1958 Nara explosion 0 0 N/A

1960 Tokyo explosion 0 0 N/A

1962 Tokyo explosion 0 0 N/A

1964 Tokyo explosion 19 114 N/A

1964 Tokyo explosion 0 0 N/A

1965 Tokyo explosion 0 0 N/A

1978 Kanagawa explosion 0 0 N/A

1979 Taiwan explosion 49 33 storage

1981 Taiwan explosion 3 1 distillator

1982 Taiwan explosion 55 5 reactor

1986 Taiwan explosion 0 0 reactor

1987 Taiwan explosion 20 0 tank

1988 Taiwan explosion 19 0 tank

1989 Taiwan fire 0 0 tank

1989 Taiwan explosion 0 0 tank

1989 Taiwan explosion 5 7 tank

1996 Taiwan explosion 47 10 tank

2000 Korea explosion 11 3 storage

2008 Taiwan explosion 0 0 reactor

2009 Taiwan explosion 0 0 reactor

2010 Taiwan explosion 0 0 reactor

Table 2.

Results of Various DSC Tests of TBHP with Scanning Rates of 1, 2, 4, and 8 °C/min and under Different Isothermal Conditions of 125, 130, 135, and 140 °C

Remarks: mass = sample mass; iso = isothermal; non-iso = non-isothermal; max = maximum heat flow.

mass (mg) non-iso (°C/min) T

(°C) ΔH

(kJ/kg)

2.8 1 134.9 883.6

2.6 2 142.5 999.0

3.3 4 149.1 746.2

2.9 8 158.8 956.9

mass (mg) iso (°C) max (mW) ΔH

(kJ/kg)

2.5 125 2.82 776.9

2.3 130 2.79 708.3

2.7 135 5.62 730.6

2.3 140 3.88 718.6

Table 3.

Results of Hazardous Reaction of TBHP Mixed with Various Protic Acids by DSC Non-isothermal

tests sample mass (mg) mixed material ΔH

(kJ/kg)

6.2 6N HNO

2073.4

6.7 6N H

SO

1113.4

7.1 6N H

PO

1126.2

Table 4.

Results of Thermal Runaway Reaction of TBHP and Mixed with Various Protic Acids by VSP2 Tests

Remarks: TBHP = original TBHP 15 mass% (20 mL).

sample T

(°C) P

(bar) (dP/dt)

(bar/min) (dT/dt)

(°C/min)

TBHP 243.9 33.3 1.9 84.9

TBHP + 6N HNO

(4 mL) 219.3 42.6 2469.5 3448.3

TBHP + 6N H

SO

(4 mL) 286.5 23.0 1642.9 5186.6

TBHP + 6N H

PO

(4 mL) 163.7 11.4 0.3 42.9

Table 5.

Comparisons of TBHP’s Kinetic Parameters for the Evaluation of N-th Order and Autocatalytic Models under Non-isothermal Condition

heating condition 1 2 4 8

kinetic model n-th auto n-th auto n-th auto n-th auto

ln(k

)/ln (sec

) 25.0

9 21.09 25.42 22.73 26.6

4 20.76 25.31 21.36

E

(kJ/mol) 107.

88 94.09 108.59 97.51 112.

15 90.17 107.8

6 92.26

nth order/n auto order/n

0.72 0.90 0.72 1.12 0.72 0.96 0.75 1.06

n

N/A 0.60 N/A 0.86 N/A 0.52 N/A 0.67

z N/A 0.40 N/A 0.26 N/A 0.11 N/A 0.22

ΔΗ

(kJ/kg) 898.

69 890.13 1022.0

5 1006.95 761.

22 750.78 983.5

2 971.89

Remark: auto=autocatalytic reaction.

Table 6.

Comparisons of TBHP’s Kinetic Parameters for the Evaluation of N-th Order and Autocatalytic Models under Isothermal Condition

isothermal 125 130 135 140

kinetic model n-th auto n-th auto n-th auto n-th auto

ln(k

)/ln (sec

) 28.18 22.13 37.8

3 22.00 31.39 22.68 23.48 22.43

E

(kJ/mol) 114.62 90.67 148.

78 91.25 126.63 91.86 105.0

6 89.93

nth order/n

auto order/n1 0.71 1.83 0.83 2.99 0.69 2.48 0.244

2 2.99

auto order/n

N/A 0.55 N/A 0.46 N/A 0.70 N/A 0.63

z N/A 1.376E-

03 N/A 3.247E-

04 N/A 1.591E-04 N/A 1.001E-08 ΔΗ

(kJ/kg) 706.68 708.29 583.

40 684.53 787.62 820.48 371.6

5 631.69

Remark: auto=autocatalytic reaction

Table 7.

The Kinetic Parameters Evaluated for TBHP Mixed with Various Protic Acids by Non-isothermal Autocatalytic Model Simulation

Remarks: auto=autocatalytic reaction; + = TBHP mixed with.

sample + 6N HNO

+ 6N H

SO

+ 6N H

PO

ln(k

)/ln (sec

) 19.21 21.47 30.57

E

(kJ/mol) 81.95 92.55 123.54

nth order/n

auto order/n1 2.46 1.86 2.35

auto order/n

0.40 0.22 0.88

z 0.01 0.02 0.02

ΔΗ

(kJ/kg) 1644.67 1116.97 1020.43

Table 8.

The Kinetic Parameters Evaluated for TBHP and Mixed with Various Protic Acids by Adiabatic

Autocatalytic Model Simulation

remarks: auto=autocatalytic reaction; + = 15 mass% TBHP mixed with.

sample 15 mass% TBHP + 6N HNO

+ 6N H

SO

+ 6N H

PO

ln(k

)/ln (sec

) 41.91 33.72 43.54 7.80

E

(kJ/mol) 108.50 75.07 121.50 204.00

nth

auto/n

0.52 1.68 0.56 1.00

auto order/ 0.31 0.85 0.33 0.06

z 0.02 9.055E-03 0.77 3.000E-03

ΔΗ

(kJ/kg) 169.92 89.91 176.55 100.00

Figure captions

Figure 1. a) A thermal explosion and runaway reaction of organic peroxide at Taoyuan

county that killed 10 people (including 6 fire fighters) and injured 47 in Taiwan in 1996.10.07.

b) Thermal runaway reaction and explosion accidents of organic peroxides (2010.01.08 Taiwan).

Figure 2. DSC curves of heat flow versus temperature for TBHP decomposition with scanning rates of 1, 2, 4, and 8 °C/min.

Figure 3. DSC curves of heat flow versus temperature for TBHP decomposition with isothermal temperature at 125, 130, 135, and 140 °C.

Figure 4. DSC non-isothermal curves of heat flow versus temperature for TBHP mixed with various protic acids decomposition with scanning rate 4 °C/min.

Figure 5. Temperature versus time for thermal runaway reaction of TBHP with various protic acids by VSP2.

Figure 6. Pressure versus time for thermal runaway reaction of TBHP with various protic acids by VSP2.

Figure 7. Inhibitive and hazardous reaction assessment of TBHP mixed with various protic acids time until the maximum rate by DSC non-isothermal.

Figure 8. Inhibitive and hazardous reaction assessment of TBHP mixed with various protic acids total energy release by DSC non-isothermal tests.

Figure 9. Inhibitive and hazardous reaction assessment of TBHP mixed with various protic acids

time until 10 % conversion with DSC non-isothermal tests.

Figure 1. a) A thermal explosion and runaway reaction of organic peroxide at Taoyuan

county that killed 10 (including 6 fire fighters) and injured 47 people in Taiwan in 1996.10.07.

b) Thermal runaway reaction and explosion accidents of organic peroxides (2010.01.08 Taiwan).

Figure 2. DSC curves of heat flow versus temperature for TBHP decomposition with scanning rates

of 1, 2, 4, and 8 °C/min.

Figure 3. DSC curves of heat flow versus temperature for TBHP decomposition with isothermal temperature at 125, 130, 135, and 140 °C.

Figure 4. DSC non-isothermal curves of heat flow versus temperature for TBHP mixed with various

protic acids decomposition with scanning rate 4 °C/min.

Figure 5. Temperature versus time for thermal runaway reaction of TBHP with various protic acids by VSP2.

Figure 6. Pressure versus time for thermal runaway reaction of TBHP with various protic acids by

VSP2.

Figure 7. Inhibitive and hazardous reaction assessment of TBHP mixed with various protic acids time until the maximum rate by DSC non-isothermal.

Figure 8. Inhibitive and hazardous reaction assessment of TBHP mixed with various protic acids

total energy release by DSC non-isothermal tests.

Figure 9. Inhibitive and hazardous reaction assessment of TBHP mixed with various protic acids

time until 10 % conversion with DSC non-isothermal tests.