Applied Catalysis A: General 219 (2001) 131140

Low temperature hydrocracking of n-heptane over Ni-supported catalysts: study of global kinetics
K.I. Alhumaizi a, , V.M. Akhmedov b , S.M. Al-Zahrani a , S.H. Al-Khowaiter b
a b

Chemical Engineering Department, King Saud University, P.O. Box 800, Riyadh 11421, Saudi Arabia Petroleum & Petrochemical Research Institute, KACST, P.O. Box 6086, Riyadh 11442, Saudi Arabia Received 28 September 2000; received in revised form 2 March 2001; accepted 8 May 2001

Abstract Two kinetic models were applied to n-heptane hydrocracking on a Ni-Re/ZSM-5 catalyst over a wide range of operating experimental conditions (temperature = 433493 K, and pressure = 760 mm Hg). In the rst model, the hydrogen is adsorbed on the catalyst surface without dissociation, while the second model assumes hydrogen dissociation. Both models assume that the adsorption follows Langmuir isotherm. The molecular hydrogen associated with an active site is most likely involved in the CC bond rupture, which is concluded to be the rate controlling step in this work. The extracted intrinsic kinetics were estimated via the derivation of the reactor model. The apparent activation energy for n-heptane cracking is found to be 83 kJ/mol. Both models describe well the n-heptane consumption rate. The simulation results revealed that the hydrogen adsorption constant is smaller than the n-heptane adsorption constant. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Hydrocracking; n-Heptane; Intrinsic kinetics; Nickel-supported catalyst

1. Introduction Hydrocracking reactions are of great importance in the petroleum rening industry for gasoline production [14]. These reactions have been investigated over a variety of catalysts by many authors [516]. Current hydrocracking processes are based on commercial catalysts that are effective above 673 K. Developing a new catalyst which works at lower temperature will increase the operational and economical benets of hydrocarcking processes. Akhmedov and others have used metal vapor methods to design new transition-metal-supported catalysts [1720]. These catalysts posses high activity
Corresponding author. Tel.: +966-1-4676873; fax: +966-1-4678-770. E-mail address: humaizi@ksu.edu.sa (K.I. Alhumaizi).

and selectivity in hydrocracking of saturated hydrocarbons under very mild conditions (less than 473 K and normal pressure). As reported by Akhmedov et al. [19], the new approaches to the preparations of metal-supported systems completely changed the reactivity and selectivity of nickle-containing catalysts with regard to known successive demethylation of alkanes [59]. n-Heptane has been widely used in catalytic transformations of alkanes as a probe molecule, due to the variety of reaction paths that it can take on different catalysts. Rearrangement of n-heptane in the presence of hydrogen over Ni-Re/ZSM-5 results in formation of only propane and i-butane. The molar distribution of the cracked products does not change signicantly even at conversions of n-heptane over 80% [19]. The mechanisms of hydrocracking reactions are directly related to the structure of the surface inter-

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 6 7 5 - 5

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mediate species that undergo rupture of CC bonds. Based on these facts, it is very important to determine the kinetics of the hydrocracking and to discuss the possible reaction mechanisms to develop these catalytic systems while seeking the optimum activity. The purpose of this work is to develop kinetic models of hydrocracking of n-heptane over Ni-Re/ZSM-5 catalyst, which reect the physiochemical nature of the process, in order to provide a better insight into the CC bond cleavage in hydrogenolysis reactions. The developed models will be used to interpret the experimental results via rate equations for the hydrocracking reactions, which can be used later for reactor design and optimization.

2. Experimental The experiments were performed in a ow reaction apparatus at atmospheric pressure. The metal vapor method (MVM) was used for preparation of Ni-Re bimetallic supported catalysts. The previous publication [19] demonstrated that the MVM is one of the most promising approaches to the synthesis of the Ni-Re/ZSM-5 catalyst which possesses unusual low

temperature CC bond cleavage activity. The details of the catalyst preparation and characterization of Ni-Re/ZSM-5 catalyst can be found elsewhere [19]. The conversion rate of n-heptane was obtained by the summation of the formation rate of all the products. The hydrogen was always kept owing through the catalyst bed. Under these conditions, no signicance deactivation of the catalyst was observed. The effects of the temperature, hydrogen and n-heptane ow rates on the conversion rate of hydrocarbon were investigated. The following experimental conditions were used for a typical catalyst run: the ne powder catalyst sample (0.2 g) was loaded into the micro-ow reactor and a thermocouple was placed on the center of the catalyst bed to monitor the reaction temperature. n-Heptane and hydrogen were fed continuously to the reactor and all the reaction products were analyzed by an online gas chromatograph (Varian Star 3600 CX) using a DBI capillary column (30 m long). Under the given conditions, n-heptane underwent hydrocracking to propane and i-butane and traces of other alkanes. The catalyst also causes isomerization of n-heptane to i-heptane. Tables 14 show the hydrocracking and hydroisomerization activity and selectivity of the studied catalyst under different reaction conditions.

Table 1 Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at different reaction temperatures Temperature (K) 433 FC7 (mole/h) FH2 (mole/h) Rtotal (mole/mole Ni h) Rcracking (mole/mole Ni h) Risomer (mole/mole Ni h) Products C1 C2 C3 i-C4 n-C4 i-C5 n-C5 i-C6 n-C6 i-C7 2Rcracking + Risomer Products 0.024 0.162 7.61 0.68 6.93 0.66 0.66 6.93 8.29 8.25 443 0.0246 0.162 24.25 6.97 17.28 0.25 6.56 6.66 0.09 0.15 17.28 31.22 30.85 453 0.0246 0.162 74.67 34.18 40.48 4.76 31.23 30.61 2.25 40.48 108.84 109.33 463 0.0246 0.162 128.4 71.19 57.22 8.50 65.63 63.52 4.78 57.22 199.60 199.65 473 0.0246 0.162 204.9 150.33 54.65 23.06 1.84 130.71 129.59 2.19 0.28 2.53 1.57 10.15 54.65 353.31 356.57 483 0.0246 0.162 313.4 240.83 72.58 36.04 6.37 214.62 198.75 4.64 0.52 4.13 3.71 16.5 72.58 552.57 557.86 493 0.0246 0.162 380.4 344.64 35.84 40.90 9.13 320.21 273.03 22.56 0.84 11.78 2.65 13.54 35.84 725.12 730.48

K.I. Alhumaizi et al. / Applied Catalysis A: General 219 (2001) 131140 Table 2 Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at T = 493 K Temperature (K) 493 FC7 (mole/h) FH2 (mole/h) Rtotal (mole/mole Ni h) Rcracking (mole/mole Ni h) Risomer (mole/mole Ni h) Products C1 C2 C3 i-C4 n-C4 i-C5 n-C5 i-C6 n-C6 i-C7 2Rcracking + Risomer Products 0.0082 0.162 140.96 125.23 15.67 25.27 2.39 105.99 101.69 2.23 0.44 2.60 3.06 7.8115 15.67 266.13 267.15 493 0.0164 0.162 275.85 246.38 29.47 30.82 6.19 213.51 195.35 14.46 6.01 4.17 17.09 29.47 522.23 517.07 493 0.0246 0.162 380.48 344.64 35.84 40.90 9.13 320.21 273.03 22.56 0.84 11.78 2.65 13.54 35.84 725.12 730.48 493 0.0246 0.324 364.78 329.91 34.87 35.79 8.26 301.27 259.05 27.67 1.01 13.83 3.01 15.95 34.87 694.69 700.71 493 0.0246 0.486 325.78 289.26 36.52 28.30 5.86 264.92 228.38 18.86 0.86 11.35 1.59 18.98 36.52 615.04 615.62 493

133

0.0246 0.648 285.74 247.34 38.50 24.48 4.85 219.49 207.63 10.44 22.33 38.50 533.18 527.72

Table 3 Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at T = 483 K Temperature (K) 483 FC7 (mole/h) FH2 (mole/h) Rtotal (mole/mole Ni h) Rcracking (mole/mole Ni h) Risomer (mole/mole Ni h) Products C1 C2 C3 i-C4 n-C4 mvci-C5 n-C5 i-C6 n-C6 i-C7 2Rcracking +Risomer Products 0.0082 0.162 110.76 87.16 23.60 16.27 1.81 77.55 75.19 1.79 0.32 1.73 1.14 5.17 23.60 197.92 204.48 483 0.0164 0.162 226.10 178.74 47.36 30.01 4.28 151.83 150.20 3.11 0.62 2.91 3.04 11.03 47.36 404.84 404.48 483 0.0246 0.162 313.42 240.83 72.59 36.04 6.37 214.62 198.75 4.64 0.52 4.13 3.71 16.50 72.58 554.25 557.86 483 0.041 0.162 516.02 384.59 131.43 58.69 8.94 336.71 318.24 7.47 7.52 7.14 31.20 131.43 900.61 907.34 483 0.0246 0.405 286.78 227.82 58.96 29.24 6.31 199.63 189.47 4.15 0.39 2.74 1.99 12.87 58.96 514.6 505.75 483 0.0246 0.648 229.27 185.12 35.15 21.89 5.94 169.39 158.10 3.64 1.65 5.55 35.15 405.39 401.31

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Table 4 Hydrocracking and hydroisomerization selectivity and product distribution of Ni-Re/ZSM-5 catalysts at different reaction temperatures Temperature (K) 473 FC7 (mole/h) FH2 (mole/h) Rtotal (mole/mole Ni h) Rcracking (mole/mole Ni h) Risomer (mole/mole Ni h) Products C1 C2 C3 i-C4 n-C4 i-C5 n-C5 i-C6 n-C6 i-C7 2Rcracking + Risomer Products 0.0082 0.162 84.18 61.95 22.23 9.47 0.77 54.70 53.22 0.89 0.11 4.04 0.64 4.17 22.43 146.13 150.44 473 0.0164 0.162 145.85 100.45 45.40 14.76 1.31 95.13 89.06 1.51 1.17 0.54 5.95 45.40 246.3 248.83 473 0.0246 0.162 204.89 150.33 54.56 23.06 1.84 130.77 128.66 2.19 0.28 2.53 1.57 10.15 54.65 355.22 355.61 463 0.0246 0.162 128.41 71.19 57.22 8.50 65.63 63.52 4.78 57.22 199.6 199.65 463 0.0328 0.162 172.11 94.82 76.29 11.34 87.47 84.64 6.37 76.29 265.93 266.11

3. Reaction mechanism and kinetics Two kinetic models were investigated to predict the overall consumption of n-heptane. Both models assume that the surface reaction is the rate-limiting step. The major difference between the two models is related to the way that hydrogen is adsorbed on the catalyst surface. In the rst model, the hydrogen is adsorbed without dissociation, while the second model assumes hydrogen dissociation. 3.1. Kinetic model I The rst kinetic model is based on a surface reaction mechanism without hydrogen dissociation. The model will be used to express the overall rate of consumption of n-heptane. The following assumptions are used to derive the kinetic model: equal competition for the active sites between the n-heptane and hydrogen in which both adsorbed on the same type of site and according to the Langmuir isotherm [21,22]; fast chemisorption of the hydrocarbon and hydrogen, without hydrogen dissociation;

surface reaction between the adsorbed reactants (n-heptane and hydrogen) is the rate-limiting step; and weak adsorption of products. The proposed reaction mechanism, based on the Langmuir adsorption isotherm approach consists of the following steps: (a) Reactant adsorption A + X AX H + X HX (b) Surface reaction AX + HX Products + 2X Here, A: n-heptane, H: hydrogen, P: product and X is the active site. AX and HX are the adsorbed n-heptane and hydrogen, respectively. Since the CC bond rupture is the rate limiting step (rls), then the reaction rate of n-heptane (i.e. surface reaction) is: rA (mole/g cat h) = kr AX HX (1)

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135

where kr is the rate constant of the surface reaction and AX and HX are n-heptane and hydrogen coverages, respectively. The coverage of the active sites is given by AX = HX = K A PA 1 + K H PH + K A P A KH P H 1 + K H PH + K A P A (2) (3)

where i: n-heptane and hydrogen, Eapp the apparent activation energy and Hi is the heat of adsorption for component i. 3.2. Kinetic model II This model assumes hydrogen dissociation on the active sites. The reaction mechanism consists of the following steps: (c) Reactant adsorption A + X AX H2 + 2X 2HX (d) Surface reaction (rls) AX + 2HX Products + 3X The consumption rate of n-heptane will have the following form. kPA PH rA = (8) (1 + KA PA + KH PH )2 4. Results and discussion Fig. 1 shows the distribution of the products obtained by hydrocracking of n-heptane on Ni-Re/

Therefore, the reaction rate of n-heptane in terms of observable gas phase partial pressure will have the following form: k r K A K H PA PH rA = (1 + KA PA + KH PH )2 (4)

PA is the partial pressure of n-heptane in the gas phase, PH is the partial pressure of hydrogen in the gas phase. This can be written in the form: rA = where k = k0 eEapp /RT and Ki = K0i e
Hi /RT

kPA PH (1 + KA PA + KH PH )2

(5)

(6)

(7)

Fig. 1. The product distribution of hydrocracking of n-heptane on Ni-Re/ZSM-5 catalyst vs. the reaction temperature.

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Fig. 2. Isomerization and cracking products of n-heptane on Ni-Re/ZSM-5 catalyst vs. the reaction temperature.

ZSM-5 catalyst versus the reaction temperature. This gure reects the fact that the product contains almost an equal molar ratio of i-butane and propane. These hydrocracking products are the major reaction products as can be seen from Figs. 1 and 2. So the Ni-Re/ZSM-5 catalyst demonstrates high internal CC bond rupture; the total number of moles in the inlet to the reactor are the same as those exit form the reactor, as shown in Tables 14. Since the temperature and the pressure along the micro xed bed can be assumed to be uniform due to the small amount of the catalyst used (0.10.2 g), the volumetric ow rate along the reactor will remain constant as illustrated in Tables 14. Fig. 2 illustrates that on increasing the temperature of the reaction, the cracking selectivity increases and the fraction of C3 and C4 represent more than 90% of the all the cracking products. Other cracking products are also obtained as a result of CC bond cleavage in the initial step of the reaction. The ratio of isomerized to cracked n-heptane decreases when conversion increases. Fig. 3 shows the Arrhenius-type diagram of the Ni-Re/ZSM-5 catalyst (i.e. the natural logarithm of the n-heptane conversion rate versus 1/T). The slope of the curve is the same for all the points corresponding to the temperature range investigated in this work; this indicates that no diffusional phenomenon occurs

( i.e. the potential required to provide the diffusion ux is insignicant) under the reaction conditions and that the reaction is kinetic-controlled. Therefore, the effectiveness factor () which accounts for the effect of diffusion is equal to 1 for such a system. One of the main causes for such reaction to be controlled by the kinetics is the usage of small catalyst particle size, which was used in this work. The results illustrated in Fig. 3 strength the hypothesis stated in the previous publications [19] which indicates that the low temperature efciency of Ni-Re/ZSM-5 catalyst could be due to the highest dispersed state of supported metal particles. In order to estimate the kinetic data, the reactor model was used. Since the laboratory reactor model is equivalent to a plug ow reactor, all molecules have same residence time and concentrations vary only along the tubular reactor. In this type of reactor, the efuent composition is an overall integral composition. The molar balance equation on a differential element of the reactor is similar to the tubular reactor design equation [23,24]: dnA = rA dW where = 1 as stated above. (9)

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Fig. 3. Total consumption rate of n-heptane vs. (1/T) over Ni-Re/ZSM-5 catalyst.

This equation relates the changes of the moles of the reactant along the reactor length (in terms of the catalyst weight) to the rate of consumption of the reactant. The kinetic model for our system is in the form of a differential equation which in some cases (i.e. low conversion) can be simplied to algebraic form. However, in this work the integral from of the above differential equation was used to determine the kinetic parameters because of higher conversion, which was calculated according to xA = nAf nA nAf (10)

where Q is the total volumetric ow rate in the reactor, T the temperature, and R is the universal gas constant.The total pressure is given by Pt Q = nT RT (14)

Therefore, using Eqs. (13) and (14), the n-heptane partial pressure can be expressed by PA = yAf (1 xA )Pt (15)

and with the same approach the hydrogen partial pressure can be expressed by PH = yHf yAf xA Pt (16)

The molar ow rates of A (n-heptane) and hydrogen (H) are nA = nAf (1 xA ), nH = nHf nAf xA (11)

where nAf and nHf are the number of moles of n-heptane and hydrogen in the feed, respectively. The reactor model equation in terms of the conversion is given by dxA rA = dW nAf (12)

The n-heptane partial pressure can be related to the its conversion by the following relation: PA = nAf (1 xA ) RT Q (13)

where yAf and yHf are the mole fractions for n-heptane and hydrogen in the feed, respectively. The nonlinear differential equation for the reactor needs to be integrated knowing the initial reactor conditions: at W = 0; XA = 0. The objective is to determine the kinetic parameters listed on the rate and reactor design equation, which will be used to predict the reactor output conditions. Therefore, the problem requires a combination of nonlinear differential equation solver technique and nonlinear regression analysis technique. For this objective, SCIENTIST software was used to solve the problem, it combines RungeKutta method with the least square approximation technique to solve for the best tting kinetic parameters.

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Fig. 4. Predicted conversion (symbol) using kinetic parameters of model I vs. the experimental conversion.

Fig. 4 shows the predicted conversion using kinetic parameters of model I versus the experimental conversion. The gure indicates that the model I predicts the n-heptane conversion quite well. The simulation results revealed that the hydrogen adsorption constant is very small compared to the n-heptane adsorption constants, which indicate the weak adsorption of hydrogen and strong adsorption of n-heptane. Therefore, the nal consumption rate of n-heptane is found to be: rA = 9.6 108 e9762/T PA PH (1 + 986.88 e3001/T PA )2 (17)

Fig. 6 shows the conversion predicted using kinetic parameters of model II versus the experimental conversion. The gure indicates that model II also predicts the n-heptane conversion quite well. The simulation results of model II also revealed that the hydrogen adsorption constant is very small compared to the n-heptane adsorption constant, which indicates the weak adsorption of hydrogen and strong adsorption of n-heptane. In this work, the hydrogen ow rate was kept much higher than the n-heptane

The apparent activation energy for this reaction is found to be 81.2 kJ/mole. The apparent activation energy value reported in the literature for n-heptane hydrocarcking on Ni-Th catalyst for producing methane and hexane is 160 kJ/mole [15]. Model I predicts a lower activation energy of n-heptane cracking to propane and butane which is in agreement with the results reported by Zahraa et al. [15]. Fig. 5 shows the n-heptane conversion versus the temperature. The solid line represents the model prediction while the symbols represent experimental data. The model predictions are very close to the experimental data specically at the higher temperature range where hydrocracking products constitute most of the products.

Fig. 5. n-Heptane conversion vs. reaction temperature, (experimental conversion: symbol, the predicted conversion: line).

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139

Fig. 6. Predicted conversion (symbol) using kinetic parameters of model II vs. the experimental conversion.

ow rate. The objective of using such high ratios of H2 /n-C7 H16 is to eliminate alkene precursors and to maintain low coke formation, since the catalyst deactivation by coke laydown is minimized by increasing H2 pressure. Therefore, the effect of using excess amounts of H2 will narrow the differences between both models, as reected on Fig. 7 by plotting the rates calculated form both mechanisms versus the

partial pressure of hydrogen. The apparent activation energy of this model is found to be 83.3 kJ/mole. Table 5 shows the kinetic parameters for both models. The nal consumption rate of n-heptane is found to be: 1.642 109 e10024/T PA PH rA = (18) (1 + 1882.3 e3206/T PA )2

Fig. 7. Predicted rates form both models vs. the partial pressure of hydrogen.

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Table 5 Kinetic parameters obtained for both models Kinetic parameters k0 (mole/g cat h) Eapp (kJ/mole) KA HA (kJ/mole) Model I 9.6 108 81.2 986.88 24.95 Model II 1.642 109a 83.3 1882.3 26.65

References
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a The value of k for model II is measured in mole atm0.5 / 0 gm cat h

5. Conclusions Adequate models describing the kinetics of hydrocracking and isomerization of n-heptane over Ni-Re/ZSM-5 catalysts were derived under the assumption that the molecular hydrogen associated with an active site is most likely involved in the CC bond rupture, which is concluded to be the rate controlling step. Experiments over a wide variety of experimental conditions were performed in a micro xed bed reactor, and kinetic parameters were estimated. The predicted conversion was found to agree well with the experimental data, providing evidence for the validity of CC bond rapture approach used here. The apparent activation energy for n-heptane cracking and isomerization is found to be 83 kJ/mole. It is concluded that the Ni-Re/ZSM-5 catalyst prepared by MVM possesses high activity and selectivity towards hydrocracking and isomerization of n-heptane. The interaction between Ni and Re seems to modify the electronic properties of Ni. In addition, such catalytic systems are highly stable with a very good activity under lower reaction temperature environments.