Coke Deposition and Structural Changes of Pellet V2O5/NaY-SiO2 in Air Regeneration: The Effects of Temperature on Regeneration

V2O5/NaY-SiO2 adsorbents were prepared by soaking up vanadium oxalate precursors into pellet NaY-SiO2. The NaY-SiO2 supports were prepared from NaY-SiO2 dough followed by extrusion and calcination at 450 °C. Ethanol was used as a model adsorbate to test the performance of the adsorbents. The regeneration efficacy, defined as the ratio of the adsorption capacity of a regenerated adsorbent to that of the fresh adsorbent, was investigated through the dynamics of fixed-bed adsorption (breakthrough curve). TPO, DSC, and FT-IR were used to characterize carbonaceous species on the adsorbents; meanwhile, synchrotron XRPD, XAS, and the N2 isotherm were used to characterize the zeolite, vanadia structure, and surface area, respectively. The results indicated that in low temperature (300 °C) regeneration, adsorption sites covered by alkylated aromatic coke formed during regeneration, causing adsorbent deactivation. In contrast, during regeneration at a high temperature (450 °C), the deactivation was caused by the destruction of the NaY framework concomitant with channel blockage, as suggested by the BET surface area combined with Rietvelt XRPD refinement results. In addition, the appearance of V-O-V contribution in the EXAFS spectra indicated the aggregation of isolated VO4, which led to a decrease in the combustion rate of the carbonaceous species deposited on the adsorbents. For regeneration at 350 and 400 °C, only trace coke formation and minor structural destruction were observed. Long-term life tests indicated that regeneration at 400 °C presents a higher maintenance of stability.

A Model of Catalytic Cracking: Catalyst Deactivation Induced by Feedstock and Process Variables

Changes in the quality of the feedstocks generated by involving various petroleum fractions in catalytic cracking significantly affect catalyst deactivation, which stems from coke formed on the catalyst surface. By conducting experimental studies on feedstocks and catalysts, as well as using industrial data, we studied how the content of saturates, aromatics and resins (SAR) in feedstock and the main process variables, including temperature, consumptions of the feedstock, catalyst and slops, influence the formation of catalytic coke. We also determined catalyst deactivation patterns using TG-DTA, N2 adsorption and TPD, which were further used as a basis for a kinetic model of catalytic cracking. This model helps predict the changes in reactions rates caused by coke formation and, also, evaluates quantitatively how group characteristics of the feedstock, the catalyst-to-oil ratio and slop flow influence the coke content on the catalyst and the degree of catalyst deactivation. We defined that a total loss of acidity changes from 8.6 to 30.4 wt% for spent catalysts, and this depends on SAR content in feedstock and process variables. The results show that despite enriching the feedstock by saturates, the highest coke yields (4.6–5.2 wt%) may be produced due to the high content of resins (2.1–3.5 wt%).

A Kinetic Model Considering Catalyst Deactivation for Methanol-to-Dimethyl Ether on a Biomass-Derived Zr/P-Carbon Catalyst

A Zr-loaded P-containing biomass-derived activated carbon (ACPZr) has been tested for methanol dehydration between 450 and 550 °C. At earlier stages, methanol conversion was complete, and the reaction product was mainly dimethyl ether (DME), although coke, methane, hydrogen and CO were also observed to a lesser extent. The catalyst was slowly deactivated with time-on-stream (TOS), but maintained a high selectivity to DME (>80%), with a higher yield to this product than 20% for more than 24 h at 500 °C. A kinetic model was developed for methanol dehydration reaction, which included the effect of the inhibition of water and the deactivation of the catalyst by coke. The study of stoichiometric rates pointed out that coke could be produced through a formaldehyde intermediate, which might, alternatively, decompose into CO and H2. On the other hand, the presence of 10% water in the feed did not affect the rate of coke formation, but produced a reduction of 50% in the DME yield, suggesting a reversible competitive adsorption of water. A Langmuir–Hinshelwood reaction mechanism was used to develop a kinetic model that considered the deactivation of the catalyst. Activation energy values of 65 and 51 kJ/mol were obtained for DME and methane production in the temperature range from 450 °C to 550 °C. On the other hand, coke formation as a function of time on stream (TOS) was also modelled and used as the input for the deactivation function of the model, which allowed for the successful prediction of the DME, CH4 and CO yields in the whole evaluated TOS interval.

Noble-Metal-Based Catalytic Oxidation Technology Trends for Volatile Organic Compound (VOC) Removal

Volatile organic compounds (VOCs) are toxic and are considered the most important sources for the formation of photochemical smog, secondary organic aerosols (SOAs), and ozone. These can also greatly affect the environment and human health. For this reason, VOCs are removed by applying various technologies or reused after recovery. Catalytic oxidation for VOCs removal is widely applied in the industry and is regarded as an efficient and economical method compared to other VOCs removal technologies. Currently, a large amount of VOCs are generated in industries with solvent-based processes, and the ratio of aromatic compounds is high. This paper covers recent catalytic developments in VOC combustion over noble-metal-based catalysts. In addition, this report introduces recent trends in the development of the catalytic mechanisms of VOC combustion and the deactivation of catalysts, such as coke formation, poisoning, sintering, and catalyst regeneration. Since VOC oxidation by noble metal catalysts depends on the support of and mixing catalysts, an appropriate catalyst should be used according to reaction characteristics. Moreover, noble metal catalysts are used together with non-noble metals and play a role in the activity of other catalysts. Therefore, further elucidation of their function and catalytic mechanism in VOC removal is required.

Nano-scale Insights Regarding Coke Formation in Zeolite SSZ-13 Subject to the Methanol-to-Hydrocarbons Reaction

The methanol-to-hydrocarbons (MTH) process, commonly catalyzed by zeolites, is of great commercial interest and therefore widely studied both in industry and academia. However, zeolite-based catalyst materials are notoriously hard to...

Mechanistic Insights into Hydrodeoxygenation of Acetone over Mo/HZSM-5 Bifunctional Catalyst for the Production of Hydrocarbons

Catalytic hydropyrolysis via the introduction of external hydrogen into catalytic pyrolysis process using hydrodeoxygenation catalysts is one of the major approaches of bio-oil upgrading. In this study, hydrodeoxygenation of acetone over Mo/HZSM-5 and HZSM-5 were investigated with focus on the influence of hydrogen pressure and catalyst deactivation. It is found that doped MoO3 could prolong the catalyst activity due to the suppression of coke formation. The influence of hydrogen pressure on catalytic HDO of acetone was further studied. Hydrogen pressure of 30 bar effectively prolonged catalyst activity while decreased the coke deposition over catalyst. The coke formation over the HZSM-5 and Mo/HZSM-5 under 30 bar hydrogen pressure decreased 66% and 83%, respectively, compared to that under atmospheric hydrogen pressure. Compared to the test with the HZSM-5, 35% higher yield of aliphatics and 60% lower coke were obtained from the Mo/HZSM-5 under 30 bar hydrogen pressure. Characterization of the spent Mo/HZSM-5 catalyst revealed the deactivation was mainly due to the carbon deposition blocking the micropores and Bronsted acid sites. Mo/HZSM-5 was proved to be potentially enhanced production of hydrocarbons.

Investigating the properties and performance of 3A molecular sieves as an adsorbent to prevent coke formation in olefin dehydration process

To study the affinity of 3A aluminosilicate adsorbents to prevent oligomerization of olefin molecules and forming green oil, physical and chemical properties of 3A molecular sieves are measured by using characterization techniques such as temperature-programmed desorption (TPD), nitrogen (N2) and water adsorptions, X-ray diffraction (XRD), X-ray fluorescence (XRF), crushing strength, and carbon dioxide (CO2) adsorption. Moreover, coke formation affinities of the understudy adsorbents are evaluated in a bench-scale system using 1-butene and 1,3-butadiene at temperatures of 220 and 260 °C, and outcomes are validated against the actual data gathered from an industrial scale olefin dehydration plant. Results confirm that the type of binder and the amount of ion exchange affect the performance of a 3A molecular sieve nominated for dehydrating olefinic streams. The binder with the least amount of acidity is preferred, and at least 35% of Na ions of the 4A zeolite should be exchanged with K ions to make it applicable for synthesizing an appropriate 3A molecular sieve. Furthermore, to control the oligomerization and inhibit green oil formation, the CO2 adsorption and acidity of Trisiv shape molecular sieves with the sizes of 1/4 inch should be less than 0.5 wt % and 1.7 mmol NH3/g, respectively. For extrudate shape with the sizes of 1/16 inch CO2 adsorption and acidity should be less than 0.2 wt % and 2.2 mmol NH3/g, respectively.

Autothermal Reforming of Acetic Acid to Hydrogen and Syngas on Ni and Rh Catalysts

The autothermal reforming (ATR) of acetic acid (HAc) as a model bio-oil compound is examined via bench scale experiments and equilibrium modelling to produce hydrogen and syngas. This study compares the performance of nickel (Ni-Al, Ni-CaAl) vs. rhodium (Rh-Al) for particulate packed bed (PPB), and of Rh-Al in PPB vs. Rh with and without Ceria for honeycomb monolith (‘M’) catalysts (R-M and RC-M). All PPB and M catalysts used Al2O3 as main support or washcoat, and when not pre-reduced, exhibited good performance with more than 90% of the HAc converted to C1-gases. The maximum H2 yield (6.5 wt.% of feed HAc) was obtained with both the Rh-Al and Ni-CaAl catalysts used in PPB, compared to the equilibrium limit of 7.2 wt.%, although carbon deposition from Ni-CaAl at 13.9 mg gcat−1 h−1 was significantly larger than Rh-Al’s (5.5 mg gcat−1 h−1); close to maximum H2 yields of 6.2 and 6.3 wt.% were obtained for R-M and RC-M respectively. The overall better performance of the Ni-CaAl catalyst over that of the Ni-Al was attributed to the added CaO reducing the acidity of the Al2O3 support, which provided a superior resistance to persistent coke formation. Unlike Rh-Al, the R-M and RC-M exhibited low steam conversions to H2 and CH4, evidencing little activity in water gas shift and methanation. However, the monolith catalysts showed no significant loss of activity, unlike Ni-Al. Both catalytic PPB (small reactor volumes) and monolith structures (ease of flow, strength, and stability) offer different advantages, thus Rh and Ni catalysts with new supports and structures combining these advantages for their suitability to the scale of local biomass resources could help the future sustainable use of biomasses and their bio-oils as storage friendly and energy dense sources of green hydrogen.