A New Catalyst on Di(1-Naphthyl)methane Hydrocracking and Kinetics Analysis

2011 ◽  
Vol 236-238 ◽  
pp. 771-774
Author(s):  
Xiao Ming Yue ◽  
Zhi Min Zong ◽  
Bing Sun ◽  
Ying Hua Wang ◽  
Yu Qing ◽  
...  

A new catalyst with two active constituents interacting with activated carbon was prepared. As a model reaction for coal liquefaction, the hydrocracking of di(1-naphthyl)methane (DNM) was investigated under different reaction conditions over the catalyst. The results show that the catalyst converts DNM hydrocraking into 1-methylnaphthalene and naphthalene with high selectively, without any hydrogenation product. Kinetic analysis indicates that DNM hydrocracking in the temperature range of 170-300 °C could be considered as a first order reaction. The activation energy E and pre-exponential factor A for DNM hydrocracking for different reaction times were calculated.

BioResources ◽  
2018 ◽  
Vol 13 (2) ◽  
pp. 4102-4117
Author(s):  
Shaoqing Wang ◽  
Xiaona Lin ◽  
Zhihe Li ◽  
Weiming Yi ◽  
Xueyuan Bai

Thermal decomposition characteristics and kinetics of high-density polyethylene (HDPE), corn stover (CS), and their blended mixture (1:1 w/w ratio) during non-catalytic and catalytic co-pyrolysis were studied via thermogravimetric analysis (TGA). The results indicated synergetic interactions between the biomass and the plastics during co-pyrolysis as measured by weight loss (ΔW); this effect was attributed to radical interactions during co-pyrolysis. The pyrolysis catalysts with higher nickel loadings (5%, 10%, and 15%) appreciably diminished the solid residue. Kinetic studies indicated that the pyrolysis was a first-order reaction based on the fitted thermogravimetric data. The activation energy (E) and pre-exponential factor (A) ranged between 26.13 kJ/mol to 392.67 kJ/mol and between 156.24 min-1 to 9.19 x 1023 min-1, respectively. There was a kinetic compensation effect (KCE) observed among the two kinetic parameters. The activation energy (E) decreased for each pyrolysis stage with the presence of a catalyst. The results indicated that catalytic co-pyrolysis could provide great potential for reducing the pyrolysis energy input.


1975 ◽  
Vol 28 (4) ◽  
pp. 759 ◽  
Author(s):  
NS Ham ◽  
JR Hall ◽  
GA Swile

A quantitative analysis of the variable-temperature 1H N.M.R. spectra of acetylacetonatotrimethyl-platinum(IV) has been made. In CDCl3 solution the exchange of acetylacetonate ligands is a first-order reaction and proceeds predominantly by dissociation of the dimer into two separated five-coordinate activated complexes. The activation energy is 61.5 � 0.8 kJ mol-1.


2010 ◽  
Vol 8 (2) ◽  
pp. 219-225
Author(s):  
Yoeswono Yoeswono ◽  
Triyono Triyono ◽  
Iqmal Tahir

A study on palm oil transesterification to evaluate the effect of some parameters in the reaction on the reaction kinetics has been carried out. Transesterification was started by preparing potassium methoxide from potassium hydroxide and methanol and then mixed it with the palm oil. An aliquot was taken at certain time interval during transesterification and poured into test tube filled with distilled water to stop the reaction immediately. The oil phase that separated from the glycerol phase by centrifugation was analyzed by 1H-NMR spectrometer to determine the percentage of methyl ester conversion. Temperature and catalyst concentration were varied in order to determine the reaction rate constants, activation energies, pre-exponential factors, and effective collisions. The results showed that palm oil transesterification in methanol with 0.5 and 1 % w/w KOH/palm oil catalyst concentration appeared to follow pseudo-first order reaction. The rate constants increase with temperature. After 13 min of reaction, More methyl esters were formed using KOH 1 % than using 0.5 % w/w KOH/palm oil catalyst concentration. The activation energy (Ea) and pre-exponential factor (A) for reaction using 1 % w/w KOH was lower than those using 0.5 % w/w KOH.   Keywords: palm oil, transesterification, catalyst, first order kinetics, activation energy, pre-exponential factor


2001 ◽  
Vol 36 (3) ◽  
pp. 589-604 ◽  
Author(s):  
Julian M. Dust ◽  
Christopher S. Warren

Abstract The kinetics of the alkaline rearrangement of O,O-dimethyl-(2,2,2-trichloro-1- hydroxyethyl)phosphonate, (trichlorfon, 1), the active insecticidal component in such formulations as Dylox, was followed at 25±0.5°C by high pressure liquid chromatography (UV-vis detector, 210 nm). The rearrangement product, O,Odimethyl- O-(2,2-dichloroethenyl)phosphate (dichlorovos, 2), which is a more potent biocide than trichlorfon, undergoes further reaction, and the kinetics, consequently, cannot be treated by a standard pseudo-first-order plot. A two-point van't Hoff (initial rates) method was used to obtain pseudo-first-order rate constants (kѱ) at 25, 35 and 45°C: 2.6 × 10-6, 7.4 × 10-6 and 2.5 × 10-5 s-1, respectively. Arrhenius treatment of this data gave an activation energy (Ea) of 88 kJ·mol-1 with a pre-exponential factor (A) of 5.5 × 109 s-1. Kinetic trials at pH 8.0 using phosphate and tris buffer systems show no buffer catalysis in this reaction and indicate that the rearrangement is subject to specific base catalysis. Estimates are reported for pseudo-first-order half-lives for trichlorfon at pH 8.0 for environmental conditions in aqueous systems in the Corner Brook region of western Newfoundland, part of the site of a recent trichlorfon aerial spray program.


1987 ◽  
Author(s):  
W Ruf ◽  
A Bender ◽  
K T Preissner ◽  
D A Lane ◽  
G Müller-Berghaus

The fibrinopeptides A and B (FPA and FPB) are cleaved from the fibrinogen molecule with different rates. In the initial phase of the thrombin-fibrinogen reaction, FPB is released with a slow rate, which is enhanced upon polymerization of desA-fi-brin monomers. The aim of the present study was to further characterize the mechanism leading to the enhanced rate of FPB release during polymerization. For this purpose, the release of FPB from normal fibrinogen and from fibrinogen London I, which exhibits a polymerization defect located in the D-domain, was studied in the presence and absence of the fibrinolytic fragment D1 (D1) and of the synthetic tetrapeptide Gly-Pro-Arg-Pro (GPRP). Steady state parameters for fibrinopeptide release were determined under pseudo-first order reaction conditions. In the initial phase of the thrombin-fibrinogen reaction, the release of FPA was unchanged in the presence of D1. Furthermore, the release of FPA from fibrinogen London I did not reveal any difference in comparison to normal fibrinogen. GPRP prevented not only fibrin polymerization, but also the enhanced rate of FPB release. On the contrary, the rate of FPB release in the presence of a 16- and 32-fold molar excess of over fibrinogen did not differ from a reaction mixture with no added D1. Si-miliar to the inhibited rate of FPB release in the presence of GPRP, the release of FPB from fibrinogen London I occurred with a slow rate, which was not enhanced by the addition of a 16-fold molar excess of D1. Since the release neither from normal fibrinogen nor from ribrinogen London I was affected by D1, it was concluded that the D-E contact formed by D1 with an E-domain of a desA-fibrin molecule does not enhance the release of FPB. While GPRP keeps fibrin in monomeric form by inhibiting the polymerization sites in the D-domains, D1 does not prevent the formation of fibrin oligomers. Therefore, acceleration of FPB release is caused by a conformational change, which is induced by binding of reciprocal polymerization sites to an E-as well as a D-domain of the same desA-fibrin molecule.


1996 ◽  
Vol 271 (3) ◽  
pp. L464-L469
Author(s):  
A. Papapetropoulos ◽  
L. A. Elmore ◽  
J. D. Catravas

It is unclear whether all or a fraction of the capillary plasma volume (Vcp) serves as the reaction volume (Vr) for pulmonary capillary endothelial ectoenzymes, in vivo. Cultured endothelial cell (EC) monolayers provide a convenient model for studying EC-bound enzyme-Vr relationships. Because the Michaelis-Menten parameter [maximum velocity of enzyme reaction (Vmax) = E x kcat/Vr, where E is enzyme mass and kcat is the constant of product formation] is inversely proportional to Vr, we hypothesized that increasing the volume of medium (Vm) bathing EC monolayers would proportionally reduce the calculated Vmax (or Vmax/K(m), where K(m) is the Michaelis constant) values of an ectoenzyme reacting with a substrate only if, and as long as, Vm = Vr. To test this hypothesis, studies were performed in bovine pulmonary arterial EC grown to confluence. Activities of angiotensin-converting enzyme (ACE) and 5'-nucleotidase (NCT) were assayed in Earle's balanced salts solution utilizing [3H]benzoyl-Phe-Ala-Pro ([3H]BPAP) and 5'-[14C]AMP as substrates, respectively. Under first-order reaction conditions and at constant substrate concentrations ([BPAP] = 15 nM, [AMP] = 1 microM), Vmax/K(m) ratios of ACE and NCT declined to 20% of their original values, as Vm increased from 0.6 to 2 ml. ACE activity was also studied at constant substrate mass (BPAP = 7 pmol) under first-order reaction conditions. Again, enzyme activity (Vmax/K(m)) declined proportionally to increasing Vm. Under zero-order reaction conditions ([BPAP] = 250 microM), ACE activity (Vmax) was similarly related to Vm. Linear regression analyses revealed that ACE or NCT would recognize up to at least 3 ml Vm, a volume vastly exceeding that of Vcp in a section of the capillary bed composed of an equivalent number of ECs, thus suggesting that Vcp could serve as the reaction volume for pulmonary capillary EC ectoenzymes in vivo.


2011 ◽  
Vol 396-398 ◽  
pp. 1803-1806
Author(s):  
Yong Chen ◽  
Lei Hong ◽  
Wei Shi ◽  
Wei Qing Han ◽  
Lian Jun Wang

The constructed Sb-doped SnO2 electrode was obtained for electrochemical degradation of RDX. The influences of current density and initial concentration of RDX on electrochemical degradation of RDX were studied. Kinetics analysis shows that the electrochemical degradation of RDX follows the pseudo first-order reaction. The mechanism of electrochemical degradation of RDX was also discussed.


2011 ◽  
Vol 233-235 ◽  
pp. 481-486
Author(s):  
Wen Bo Zhao ◽  
Ning Zhao ◽  
Fu Kui Xiao ◽  
Wei Wei

The synthesis of dimethyl carbonate (DMC) from urea and methanol includes two main reactions: one amino of urea is substituted by methoxy to produce the intermediate methyl carbamate (MC) which further converts to DMC via reaction with methanol again. In a stainless steel autoclave, the kinetics of these reactions was separately investigated without catalyst and with Zn-containing catalyst. Without catalyst, for the first reaction, the reaction kinetics can be described as first order with respect to the concentrations of methanol and methyl carbamate (MC), respectively. For the second reaction, the results exhibit characteristics of zero-order reaction. Over Zn-containing catalyst, the first reaction is neglected in the kinetics model since its rate is much faster than second reaction. After the optimization of reaction condition, the macro-kinetic parameters of the second reaction are obtained by fitting the experimental data to a pseudo-homogenous model, in which a side reaction of DMC synthesis is incorporated since it decreases the yield of DMC drastically at high temperature. The activation energy of the reaction from MC to DMC is 104 KJ/mol while that of the side reaction of DMC is 135 KJ/mol.


1989 ◽  
Vol 163 ◽  
Author(s):  
Masashi Suezawa ◽  
Koji Sumino

AbstractThe generation and dissociation processes of Fe-B pairs in Si crystal are investigated by means of the measurements of electron paramagnetic resonance of Si crystals of various B concentrations doped with Fe. Fe-B pairs are generated due to annealing of the crystals at temperatures around 300 K obeying to the first order reaction kinetics. The activation energy for pair generation is determined to be about 0.65 eV which is almost equal to the migration energy of Fe impurity in a Si crystal. Fe-B pairs are found to be dissociated at tempeatures higher than 150°C leading to the precipitation of Fe.


2014 ◽  
Vol 44 (3) ◽  
pp. 195-201
Author(s):  
L. KUNIGK ◽  
S. P. GALIZIA ◽  
R.T. K. SHIKISHIMA ◽  
R. GEDRAITE ◽  
C. H. JURKIEWICZ

Peracetic acid (PAA) is a strong oxidant used by the food industry as a sanitizer, in medical area as a disinfectant and by the textiles and paper industries as a bleacher. Its decomposition rate is an important parameter in these applications. The main purpose of this paper is to study the decomposition kinetics of PAA between 25 and 45 °C in solutions with pH 3.11, 5.0 and 7.0. The decomposition of PAA is a first-order reaction for all solutions and temperatures studied. The rate constants were between 2.08·10-3 and 9.44·10-3 h-1 (pH 3.11), between 2.61·10-3 and 16.69·10-3 h-1 (pH 5.0) and between 7.50·10-3 and 47.63·10-3 h-1 (pH 7.0). The activation energy of PAA decomposition in aqueous solutions are 58.36 and 72.89 kJ·mol-1 when pH was 3.11 and 5.0, respectively.


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