Temperature Programmed Oxidation as an Analysis Technique for Deactivated Hydrotreating Catalysts

Author(s):  
J. van Doorn ◽  
J.L. Bosch ◽  
R.J. Bakkum ◽  
J.A. Moulijn
2005 ◽  
Vol 17 (15) ◽  
pp. 3935-3943 ◽  
Author(s):  
A. Tschöpe ◽  
J. Markmann ◽  
P. Zimmer ◽  
R. Birringer ◽  
Chadwick

2002 ◽  
Vol 505 ◽  
pp. 58-70 ◽  
Author(s):  
D.T.P. Watson ◽  
J.J.W. Harris ◽  
D.A. King

2010 ◽  
Vol 3 (2) ◽  
pp. 118-125
Author(s):  
Hery Haerudin ◽  
Silvester Tursiloadi ◽  
Galuh Widiyarti ◽  
Wuryaningsih Sri Rahayu

Nickel catalyst has been prepared impregnation and precipitation with nickel content of 20% and 25% each using bentonite as support material. The effects of the preparation method were studied using temperature programmed oxidation (TPO) and temperature programmed reduction (TPR) and by determination of its specific surface area. The activity of catalysts has been tested in the hydrogenation of palm oil. The catalyst with 20% of nickel and prepared by impregnation shows a single peak at 301°C, compared to catalyst with 25% of nickel prepared by the same method which has a peak at 304°C and a shoulder at 330°C. The reduction curves of both catalysts, those are prepared by impregnation, show a homogeneity indicated by a high main peak at 426°C (20% Ni) and 430°C (25% Ni). The 25% nickel catalyst by impregnation has a shoulder at 508°C. The catalysts prepared by precipitation show peaks at 508°C and 661°C for 20% of Ni and peaks at 419°C and 511°C for 25% of Ni. The reduction curves of catalysts prepared by precipitation are significantly different from each other. Those are also very different comparing to the reduction curve of impregnated catalyst. The 20% precipitated nickel catalyst has a single peak at 540°C, but the 25% precipitated nickel catalyst shows peaks at 346°C and 503°C. The differences of peak position among the reduction curves of catalysts resulted in the differences of catalyst activities with the following order 20% Ni (impregnation) > 25% Ni (impregnation) > 20% Ni (precipitation) > 25% Ni (precipitation).   Keywords: bentonite, nickel catalyst, hidrogenation


Catalysts ◽  
2020 ◽  
Vol 10 (5) ◽  
pp. 584
Author(s):  
Kathleen Kirkwood ◽  
S. David Jackson

The hydrogenation and hydrodeoxygenation (HDO) of dihydroxybenzene isomers, catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene) and hydroquinone (1,4-dihydroxybenzene) was studied in the liquid phase over a Rh/silica catalyst at 303–343 K and 3 barg hydrogen pressure. The following order of reactivity, resorcinol > catechol > hydroquinone (meta > ortho > para) was obtained. Kinetic analysis revealed that catechol had a negative order of reaction whereas both hydroquinone and resorcinol gave positive half-order suggesting that catechol is more strongly adsorbed. Activation energies of ~30 kJ·mol−1 were determined for catechol and hydroquinone, while resorcinol gave a value of 41 kJ·mol−1. Resorcinol, and similarly hydroquinone, gave higher yields of the hydrogenolysis products (cyclohexanol, cyclohexanone and cyclohexane) with a cumulative yield of ~40%. In contrast catechol favoured hydrogenation, specifically to cis-1,2-dihydroxycyclohexane. It is proposed that cis-isomers are formed from hydrogenation of dihydroxycyclohexenes and high selectivity to cis-1,2-dihydroxycyclohexane can be explained by the enhanced stability of 1,2-dihydroxycyclohex-1-ene relative to other cyclohexene intermediates of catechol, resorcinol or hydroquinone. Trans-isomers are not formed by isomerisation of the equivalent cis-dihydroxycyclohexane but by direct hydrogenation of 2/3/4-hydroxycyclohexanone. The higher selectivity to HDO for resorcinol and hydroquinone may relate to the reactive surface cyclohexenes that have a C=C double bond β-γ to a hydroxyl group aiding hydrogenolysis. Using deuterium instead of hydrogen revealed that each isomer had a unique kinetic isotope effect and that HDO to cyclohexane was dramatically affected. The delay in the production of cyclohexane suggest that deuterium acted as an inhibitor and may have blocked the specific HDO site that results in cyclohexane formation. Carbon deposition was detected by temperature programmed oxidation (TPO) and revealed three surface species.


2020 ◽  
Vol 63 (15-18) ◽  
pp. 1446-1462 ◽  
Author(s):  
Kathryn L. MacIntosh ◽  
Simon K. Beaumont

AbstractFurfural is a key bioderived platform molecule, and its hydrogenation affords access to a number of important chemical intermediates that can act as “drop-in” replacements to those derived from crude oil or novel alternatives with desirable properties. Here, the vapour phase hydrogenation of furfural to furfuryl alcohol at 180 °C over standard impregnated nickel catalysts is reported and contrasted with the same reaction over copper chromite. Whilst the selectivity to furfuryl alcohol of the unmodified nickel catalysts is much lower than for copper chromite as expected, the activity of the nickel catalysts in the vapour phase is significantly higher, and the deactivation profile remarkably similar. In the case of the supported nickel catalysts, possible contribution to the deactivation by acidic sites on the catalyst support is discounted based on the similarity of deactivation kinetics on Ni/SiO2 with those seen for less acidic Ni/TiO2 and Ni/CeO2. Powder X-ray diffraction is used to exclude sintering as a primary deactivation pathway. Significant coking of the catalyst (~ 30 wt% over 16 h) is observed using temperature programmed oxidation. This, in combination with the solvent extraction analysis and infrared spectroscopy of the coked catalysts points to deactivation by polymeric condensation products of (reactant or) products and hydrocarbon like coke. These findings pave the way for targeted modification of nickel catalysts to use for this important biofeedstock-to-chemicals transformation.


2019 ◽  
Vol 2019 ◽  
pp. 1-9
Author(s):  
Weiqing Zhang ◽  
Shuguang Jiang ◽  
Tong Qin ◽  
Jianfeng Sun ◽  
Chaowei Dong ◽  
...  

The effects of six ionic liquids with surfactant property (1-hydroxyethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide ([HOEtMIm][NTf2]), 1-hydroxyethyl-3-methyl imidazolium tetrafluoroborate ([HOEtMIm][BF4]), 1-dodecyl-3- methyl imidazolium bromide ([C12MIm]Br), 1-tetradecyl-3- methyl imidazolium bromide ([C14MIm]Br), trioctyl methyl ammonium chloride ([N8,8,8,1])Cl, and tetraethyl ammonium chloride ([N2,2,2,2]Cl)) on the oxidation characteristics and functional groups of coal were studied by means of critical micelle concentration, surface tension, thermogravimetric analysis, temperature-programmed oxidation, and Fourier transform infrared spectroscopy (FTIR) measurements. The lower critical micelle concentration for the ionic liquids except the [N2,2,2,2]Cl suggests the favorable surface activity of these ionic liquids. The surface activities of [N8,8,8,1]Cl, [C14MIm]Br, [C12MIm]Br, and [HOEtMIm][NTf2] were high, while that of [N2,2,2,2]Cl was relatively lower. The thermal stabilities of [HOEtMIm][NTf2] and [HOEtMIm][BF4] were high, while those of [N8,8,8,1]Cl and [N2,2,2,2]Cl were lower. The oxidation activities of ionic liquid-mixed coals were weakened to different degrees except [N8,8,8,1]Cl-mixed coal, because of the poor thermal stability and decomposition of [N8,8,8,1]Cl accelerating the coal oxidation. The other five ionic liquids were suitable for inhibiting coal oxidation, particularly the [HOEtMIm][BF4] and [HOEtMIm][NTf2] with higher inhibition rate, longer inhibition time, and also better thermal stabilities. The activation energy results further confirmed such inhibition effect. The functional group results showed that treatment of ionic liquids on coal can change the contents of hydrogen bonds, aliphatic groups, and aromatic groups in coal. It was inferred that the [HOEtMIm][BF4], [HOEtMIm][NTf2], and [C14MIm]Br were more effectively to affect coal structure and decrease coal oxidation activity.


2020 ◽  
Vol 143 (3) ◽  
Author(s):  
Yansong Zhang ◽  
Houwang Wang ◽  
Wenzhou Du ◽  
Kuo Niu ◽  
Xiangrui Wei

Abstract In this study, an experimental investigation was presented on the oxidation behaviors of bituminous coal for different inert gases (N2 and CO2) at different concentrations (oxygen concentration indexes 21%, 18.4%, 15.8%, and 13.1%) using a temperature-programmed experimental device. The purpose of this research was to examine the oxidation patterns of bituminous coal under different inert conditions. The results showed that: (1) the oxidative heating of the coal underwent two stages: an initial slow heating stage and a fast heating stage. The injection of both inert gases would result in a delay in the crossing point temperature (CPT) of the coal, but the injection of N2 resulted in greater delays in the CPT of the coal; (2) the injection of both N2 and CO2 inhibited the concentrations of CO and alkane/olefin gases produced from the oxidative heating of the coal, with CO2 displaying higher inhibition efficiencies than that of N2; (3) Under a non-inerting environment, the C2H4 and C2H6 generation temperatures were 110 °C and 100 °C. Under an inerting environment, when N2 was injected, the higher the N2 concentration, the higher the initial C2H4 and C2H6 generation temperatures; when CO2 was injected, the higher the CO2 concentration, the lower the initial C2H4 and C2H6 generation temperatures; and (4) under a non-inerting environment, the C3H8 generation temperature was 90 °C; and when an inert gas was injected, there was a hysteresis in the C3H8 generation temperature for all concentrations. The above research results can be used to predict the spontaneous combustion of residual coal in an inert environment and prevent fires.


Sign in / Sign up

Export Citation Format

Share Document