Catalytic Decomposition of N2O ON ZrO2 and Co/Ni/ZrO2 Systems

1994 ◽  
Vol 344 ◽  
Author(s):  
H. C. Zeng ◽  
J. Lin ◽  
W. K. Teo ◽  
J. Wu ◽  
K. L. Tan

AbstractMonoclinic ZrO2 and its supported catalysts Co/Ni/ZrO2 for catalytic decomposition of N2O have been studied with FTIR, EDAX, XPS, and the evaluation of activity of the catalysts. It is found that monoclinic ZrO2 alone has the catalytic effect for N2O decomposition although the gas decomposes on Co/Ni/ZrO2 more efficiently. The XPS study shows that only Co exists in the surface region of ZrO2. In evaluation experiments, it is found that when Co/Ni exceeds a threshold concentration, the conversion of N2O is no longer accelerated with the increase of Co/Ni content. The gas decomposition on Co/Ni/ZrO2 can be described as first order with respect to partial pressure of N2O. No nitrogen N(ls) photoelectrons were detected for the catalysts after N2O decomposition. Surface reactions on ZrO2 and Co/Ni/ZrO2, including the behaviour of retained carbon (Cls) and N2O decomposition mechanism, will also be addressed.

1995 ◽  
Vol 10 (3) ◽  
pp. 545-552 ◽  
Author(s):  
H.C. Zeng ◽  
J. Lin ◽  
W.K. Teo ◽  
J.C. Wu ◽  
K.L. Tan

Monoclinic ZrO2 and its supported materials Co/Ni/ZrO2 (Co:Ni = 1:1) for catalytic decomposition of N2O have been studied with GC, FTIR, EDAX, XPS, and the evaluation of catalytic activity of the materials. It is found that monoclinic ZrO2 alone has the catalytic effect for N2O decomposition, although higher activities are found for Co/Ni/ZrO2 systems. XPS study shows that only Co exists in the surface region of ZrO2, which is attributed to the formation of NiO–ZrO2 solid solution resulting from an interdiffusion between Ni2+ and ZrO2 matrix. The gas decomposition on Co/Ni/ZrO2 can be described as first order with respect to partial pressure of N2O. Surface reactions on ZrO2 and Co/Ni/ZrO2 will also be addressed.


2016 ◽  
Vol 40 (3) ◽  
pp. 2904-2909 ◽  
Author(s):  
Lili Song ◽  
Chao Chen ◽  
Xiangbin Chen ◽  
Ning Zhang

MOFs exhibited different catalytic activities depending on the organic groups decorated on the pore walls, which displayed a synergetic catalytic effect.


2020 ◽  
Vol 686 ◽  
pp. 178544
Author(s):  
Rajanna Gugulothu ◽  
Arun Kumar Macharla ◽  
Kranthi Chatragadda ◽  
Anuj A. Vargeese

1975 ◽  
Vol 30 (7-8) ◽  
pp. 466-473 ◽  
Author(s):  
Hermann Esterbauer ◽  
Helmward Zöllner ◽  
Norbert Scholz

Abstract 1. GSH reacts with conjugated carbonyls according to the equation: G SH+R-CH=CH-COR⇆R-CH(SG)-CH2-COR. The forward reaction follows second order, the reverse reaction first order kinetics. It is assumed that this reaction reflects best the ability of conjugated carbonyls to inactivate SH groups in biological systems. 2. The rate of forward reaction increases with pH approx. parallel with αSH. Besides OH- ions also proton donors (e. g. buffers) increase the rate. The catalytic effect of pH and buffer is inter­ preted in view of the reaction mechanism. 3. The equilibrium constants as well as the rate constants for forward (k1) and reverse reaction show an extreme variation depending on the carbonyl structure. Acrolein and methyl vinyl ketone (kt = 120 and 32 mol-1 sec-1 , resp.) react more rapidly than any other carbonyl to give very stable adducts (half-lives for reverse reaction 4.6 and 60.7 days, resp.). Somewhat less reactive are 4-hydroxy-2-alkenals and 4-ketopentenoic acid (k1 between 1 and 3 mol-1 sec-1), but they also form very stable adducts showing half-lives between 3.4 and 19 days. All other carbonyl studied react either very slowly (e. g. citral, ethly crotonate, mesityl oxide, acrylic acid) or form very labile adducts (crotonal, pentenal, hexenal, 3-methyl-butenone). Comparing biological activities of con­ jugated carbonyls their reactivity towards HS (k1) and the stability of the adducts must be considered.


The reaction CH 3 CH(OH) 2 →CH 3 CHO + H 2 O has been studied kinetically in aqueous acetone using a dilatometric method. It was found to be a first-order reaction, catalyzed by uncharged acids, cation acids, uncharged bases and anion bases. Quantitative measurements were made on the catalytic effect of 63 acids. The results for 32 carboxylic acids and 15 phenols conform approximately to a single relation between catalytic power and dissociation constant in water, but most of the 16 acids of other types show considerable positive or negative deviations from this relation. These deviations are related to the structures of the catalysts, and it is shown that, for acids of equal strength, the velocity of protolytic change is decreased by a mesomeric charge-shift in the anion, and is increased if mesomerism in the acid is lost on ionization. This principle is related to the occurrence of pseudo-acids and bases, and is interpreted in terms of molecular potential energy curves.


Author(s):  
Matin Parvari ◽  
Peyman Moradi

The hydrodesulfurization of dibenzothiophene (HDS of DBT) in a high pressure batch reactor at 320°C was carried out over CoMo/Al2O3-B2O3 catalysts with different B2O3 contents (4, 10, and 16 wt%). Ethylenediaminetetraacetic acid (EDTA) with different EDTA/Co mole ratios (0.6, 1.2 and 1.8) was used as a chelating ligand during the preparation of CoMo/Al2O3-B2O3. XRD studies, FTIR, TPD of NH3, and BET experiments were used to investigate the catalyst samples. The results showed that the catalyst using the support with 4 wt% B2O3 and an EDTA/Co mole ratio of 1.2 had a hydrodesulfurization activity (in pseudo first order kinetic constant basis) value of ~2.96 times higher than that of the simple CoMo/Al2O3 catalyst.


2017 ◽  
Vol 197 ◽  
pp. 41-57 ◽  
Author(s):  
Saeedeh S. Tafreshi ◽  
Alberto Roldan ◽  
Nora H. de Leeuw

Hydrazine (N2H4) is produced at industrial scale from the partial oxidation of ammonia or urea. The hydrogen content (12.5 wt%) and price of hydrazine make it a good source of hydrogen fuel, which is also easily transportable in the hydrate form, thus enabling the production of H2in situ. N2H4 is currently used as a monopropellant thruster to control and adjust the orbits and altitudes of spacecrafts and satellites; with similar procedures applicable in new carbon-free technologies for power generators, e.g. proton-exchange membrane fuel cells. The N2H4 decomposition is usually catalysed by the expensive Ir/Al2O3 material, but a more affordable catalyst is needed to scale-up the process whilst retaining reaction control. Using a complementary range of computational tools, including newly developed micro-kinetic simulations, we have derived and analysed the N2H4 decomposition mechanism on the Cu(111) surface, where the energetic terms of all states have been corrected by entropic terms. The simulated temperature-programmed reactions have shown how the pre-adsorbed N2H4 coverage and heating rate affect the evolution of products, including NH3, N2 and H2. The batch reactor simulations have revealed that for the scenario of an ideal Cu terrace, a slow but constant production of H2 occurs, 5.4% at a temperature of 350 K, while the discharged NH3 can be recycled into N2H4. These results show that Cu(111) is not suitable for hydrogen production from hydrazine. However, real catalysts are multi-faceted and present defects, where previous work has shown a more favourable N2H4 decomposition mechanism, and, perhaps, the decomposition of NH3 improves the production of hydrogen. As such, further investigation is needed to develop a general picture.


1968 ◽  
Vol 8 (02) ◽  
pp. 137-148 ◽  
Author(s):  
I.S. Bousaid ◽  
H.J. Ramey

Abstract Experimental results on the oxidation reaction kinetics in the forward combustion oil recovery process are presented. A total of 48 runs were made wherein a stationary thin layer of coked, unconsolidated sand was burned isothermally in a combustion cell. Individual runs were made at various temperature levels to permit determination of the effect of temperature upon the reaction. An expression was obtained for the burning rate of carbon as a function of carbon concentration, combustion temperature and oxygen partial pressure. The carbon burning rate for two types of crude oil indicated a first order reaction with respect to both carbon concentration and oxygen partial pressure. The effect of combustion temperature on the reaction rate constant matched the Arrhenius equation. The activation energy was similar for the two crude oils examined. The activation energy decreased for a porous media containing clay. The rate of oxidation of crude oil at reservoir temperature was found to be significant. Other significant findings included information on hydrogen-carbon content of fuel residues, fuel reactivity and the products of combustion. Introduction The production of crude oil by underground combustion has been studied in the laboratory by many investigators. Results of laboratory and field experiments have been reported in the literature describing the forward combustion process. But as yet, no qualitative or quantitative study of the kinetics of fuel combustion involved in this process has been reported. The fuel concentration and the rate at which fuel is burned at the front are important factors governing the air requirement in a forward combustion operation. Although the fuel is essentially unrecoverable crude, the air required to burn the fuel is an important economic factor in this process. Because fuel is burned, the heat transport associated with forward combustion is a key and unique feature of this new oil recovery method. Many investigators have presented information on the heat transmission and fluid mechanics involved in forward combustion. Berry and Parrish demonstrated the utility of considering reaction kinetics in reverse burning. From differential thermal analysis, Tadema presented a qualitative discussion of the nature of reactions between oil and oxygen in combustion oil recovery. Although little quantitative work has been done on be reaction kinetics involved in forward combustion oil recovery, an extensive literature does exist on combustion of carbons and oils, and carbonaceous residues from cracking catalyst pellets. Dart, et al., studied the combustion rate for oxidation of carbonaceous residues on clay catalyst pellets, and found the reaction to be second-order with respect to carbon concentration, and first-order with respect to oxygen partial pressure for carbon concentrations less than 2 weight percent of the catalyst weight. The reaction appeared to be first-order with respect to carbon concentration for concentrations greater than 2 percent. Metcalfe noted that other workers had found that aging of the fuel during the combustion process was responsible for changing coke properties, and A accounted for the apparent second-order carbon concentration effect found by Dart, et al. It appears that burning of residues from cracking pellets is first-order with respect to both carbon concentration and oxygen partial pressure. Dart, et al., also observed that hydrogen in the hydrocarbon residue appeared to react faster than the carbon. Lewis, et al., studied oxidation of charcoal, coke and graphite in a fluidized bed. Gas velocities were high enough to partially lift and circulate the carbon particles. Their results indicated first-order reaction dependency with respect to both carbon concentration and oxygen partial pressure. SPEJ P. 137ˆ


2013 ◽  
Vol 662 ◽  
pp. 167-172 ◽  
Author(s):  
Xiao Lun Wang ◽  
Li Ping Liu ◽  
Hai Ming Xu

With the widely research of nano-TiO2, researchers have found another way of managing air quality. As an excellent photocatalyst material, nanometer titanium dioxide has begun to be used in road engineering in recent years. In this paper, substantial gas decomposition tests are performed utilizing the self-designed sealed container and UV aging box. At first, the catalytic efficiencies of nanometer titanium dioxide dispersed in silane solvent and in asphalt mixture were compared. The results show that nanometer titanium dioxide is able to decompose CO, HC and NO after being dispersed in silane solvent and asphalt mixture. To achieve the same catalytic efficiency, the amount of the nanometer titanium dioxide dispersed in silane solvent is much less than that in asphalt mixture. For asphalt mixture, high void fraction may mean high catalytic efficiency. Then the long-term decomposition of asphalt mixture was discussed. The asphalt mixture still has good catalytic decomposition effect after six months. The catalytic effect of asphalt mixture does not diminish over time and the effect of decomposing HC has improved after six months. At last, for cement paint, the catalytic effect of decomposing NO and HC does not diminish over time, but the effect of decomposing CO reduces.


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