The Oil Shale Transformation in the Presence of an Acidic BEA Zeolite under Microwave Irradiation

The transformation of an oil shale sample from the Autun Basin in the Massif Central, France, was studied using two different heating strategies: microwave irradiation and conventional heating. Microwave heating was performed using a single-mode cavity operating at a frequency of 2.45 GHz under an inert atmosphere. Heating of the sample generated liquid products of similar composition using either microwave or conventional heating. The yields of liquid products were similar in the two cases, while the overall energy requirements were much lower using microwave irradiation. The influence of water vapor on the oil shale decomposition was also studied under microwave energy. In order to simulate conversion of the organic fraction of the oil shale in the presence of an acidic zeolite catalyst, the oil shale sample was mixed with 5 wt % BEA zeolite and heated under microwave irradiation. It was found that the liquid products yield decreased along with an increase in the amount of coke produced. Gaseous and liquid products recovered showed a tendency for the production of lighter components in the presence of zeolite. The aromatic character of the oils was more important when microwaves were used, especially in the presence of zeolite

Infrared and microwaves at 5.8 GHz in a catalytic reactor

An improved micro-reactor cell for IR spectroscopic studies of heterogeneous catalysis was built around a 5.8 GHz microwave cavity. The reactor can operate at 20 bars and with conventional heating up to 720 K, with reactant gas flows velocities (GHSV) from 25 000 to 50 000 h−1. The temperature of the sample under microwave irradiation was measured by time resolved IR emission spectroscopy. The first experiment performed was the IR monitoring of the desorption of carbonates induced by irradiating an alumina sample by microwaves at 5.8 GHz

Probing zeolites by vibrational spectroscopies

International audienc

Isomorphous Substitution of Framework Atoms by Titanium in VPI-5 Aluminophosphate Molecular Sieve

Extra-large pore aluminophosphate molecular sieve TiVPI-5 was synthesised hydrothermally in the presence of di-n-butylamine and transformed by the calcination process at 500 °C to a large pore TAPO-8. Incorporation of titanium(IV) into VPI-5 framework was studied by elemental and thermogravimetric analyses, combined with X-ray Absorption Near Edge Structure (XANES) spectroscopy and UV-VIS absorption spectroscopy. We found that titanium(IV) incorporated in TiVPI-5 isomorphously substitutes framework aluminium on octahedral sites and that it is not present in the structure in the form of TiO2 anatase. In situ IR measurements of pyridine adsorption/desorption were used to check the presence of catalytically active centres in the product resulting from titanium incorporation into the VPI-5 framework. Weak Lewis and Brønsted acid sites were found in small amounts in the calcined product TAPO-8

On the enhancing effect of Ce in Pd-MOR catalysts for NOx CH4-SCR: a structure-reactivity study

The effect of palladium and cerium species on the selective catalytic reduction (SCR) of NOx using methane as reductant (NOx CH4-SCR) has been investigated using Pd-HMOR and PdCe-HMOR system. The catalysts have been characterised by H2-TPR, DRS UV–Vis, TEM/EDS and FTIR using CO and pyridine as probe molecules. The oxidation of NO and CH4-SCR catalytic tests have been conducted using monometallic and bimetallic formulations.Above 0.3 wt.% Pd, the increase in Pd loading leads to a decrease in NOx selectivity towards N2, with the formation of N2O, and a decrease in the CH4 selectivity towards SCR, due to CH4 direct combustion. H2-TPR and FTIR-CO studies indicate that palladium is stabilised as Pd2+ in ion-exchange position, probably in two different sites within the MOR framework.The addition of cerium to Pd-HMOR enhances its catalytic performance for NOx CH4-SCR. With 1 wt.% Ce, both NOx conversion into N2 and CH4 selectivity towards SCR have increased. Small CeO2 clusters interacting with palladium are likely to play a major role in this catalytic reaction. The number of such species increases up to Ce loading of ca. 2 wt.%. However, above 3 wt%, NOx conversion values decrease with Ce loading, which is attributed to the formation of bulk CeO2 species not interacting with palladium

Catalytic ozonation with γ-Al2O3 to enhance the degradation of refractory organics in water

Nowadays, heterogeneous catalytic ozonation appears as a promising way to treat industrial wastewaters containing refractory pollutants, which resist to biological treatments. Several oxides and minerals have been used and their behavior is subject to controversy with particularly the role of Lewis acid sites and/or basic sites and the effect of salts. In this study, millimetric mesoporous γ-Al2O3 particles suitable for industrial processes were used for enhancing the ozonation efficiency of petrochemical effluents without pH adjustment. A phenol (2,4-dimethylphenol (2,4-DMP)) was first chosen as petrochemical refractory molecule to evaluate the influence of alumina in ozonation. Single ozonation and ozonation in presence of γ-Al2O3 led to the disappearance of 2,4-DMP in 25 min and a decrease in pH from 4.5 to 2.5. No adsorption of 2,4-DMP occurred on γ-Al2O3. Adding γ-Al2O3 in the process resulted in an increase of the 2,4–DMP oxidation level. Indeed, the total organic carbon (TOC) removal was 14% for a single ozonation and 46% for ozonation with γ-Al2O3. Similarly, chemical oxygen demand (COD) removal increases from 35 to 75%, respectively. Various oxidized by-products were produced during the degradation of 2,4-DMP, but after 5 h ozonation 90% of organic by-products were acetic acid > formic acid ≫ oxalic acid. Some of the carboxylic acids were adsorbed on γ-Al2O3. The use of radical scavengers (tert-butanol) highlighted the involvement of hydroxyl radicals during catalytic ozonation with γ-Al2O3 in contrary to single ozonation, which mainly involved direct ozone reaction. γ-Al2O3 is an amphoteric solid with Lewis acid AlOH(H+) sites and basicAl-OH sites. After ozonation the amount of basic sites decreased due to carboxylates adsorption, while the Lewis acid sites remained constant as evidenced by FTIR. Several ozonation runs with γ-Al2O3 reported a progressive decrease of its catalytic activity due to the cumulative sorption of carboxylates on the basic sites. After 80 h of ozonation, a calcination at 550 °C allowed to recover allAl-OH basic sites and the initial activity of γ-Al2O3. A synthetic petrochemical effluent containing various petrochemicals (phenol, acetic acid, naphtenic acid, pyrene, naphtalene) was then treated with γ-Al2O3 with and without NaCl. Sodium ions prevented carboxylates adsorption on γ-Al2O3 leading to a higher efficiency of γ-Al2O3 in presence of NaCl and allowed to decrease the toxicity of the petrochemical effluent

Acidity and accessibility studies of desilicated ZSM-5 zeolites in terms of their effectiveness as catalysts in acid-catalyzed cracking processes

The structural, textural and acidic characteristics of hierarchical ZSM-5 (Si/Al = 18-32), obtained with two desilication approaches, and the effect of these treatments on the reactivity in various cracking reactions of variable feedstock size and severity have been investigated. Emphasis is given to understanding the accessibility of acid sites; this was investigated by textural analysis, FTIR probe molecules (pyridine, trimethylacetonitrile and 2,4,6-trimethylpyridine) and reactions involving n-decane, 1,3,5-triisopropylbenzene (TIPB), and low and high-density polyethylene, LDPE and HDPE, respectively. Higher surface areas and a narrower pore size distribution were obtained for NaOH&TBAOH-treated materials, comparing to NaOH-treated ones. FTIR studies of pivalonitrile and collidine adsorption correlate well with the mesopore surface area. For n-decane cracking activity, the acid strength is a determining factor, revealing that the NaOH&TBAOH treatment gave stronger sites than NaOH, but lower than the native zeolite. In contrast, the TIPB cracking activity was improved by the developed mesoporosity of the alkaline treated zeolites, and this was correlated to the pivalonitrile and collidine accessibility factors. During the n-decane and TIPB cracking, hydrogen transfer reactions were reduced, leading to high olefin production for the NaOH&TBAOH materials due to the shorter microporous paths after desilication. The increased accessibility of the acid sites also leads to an enhanced cracking activity of polyethylenes at low conversions, as determined by a decrease in the T5% and T50%; both parameters are linearly dependent on the pivalonitrile and collidine accessibility factors, for LDPE and HDPE. The T5% for HDPE is more influenced by the accessibility factors than it is for the LDPE. This is interpreted to be the result of the branching degree of HDPE and LDPE; linear HDPE is more sensitive to the enhanced number of pore mouths of ZSM-5 channels on the mesopores. At high conversion, the influence on the T50% of the accessibility factors for HDPE and LDPE is weaker, suggesting that the cracking at this stage involves intermediate molecules of smaller size with fewer diffusional limitations. With respect to our own prior work, the chosen zeolite and the cracking of polyolefins gave more pronounced differences for the hierarchical ZSM-5