Sulphidation of an oxidic CoMo/Al2O3 catalyst under practical conditions: different kinds of sulphur species

The sulphidation of a CoMo/Al₂O₃ hydrotreating catalyst was studied under pressure and flow conditions close to industrial practice. The sulphiding mixture contained equal amounts of H₂S and CH₄ diluted in hydrogen under 3.9 MPa total pressure. The oxidic precursor was flushed by the reagent gas at 40°C for 10 h, then the temperature was raised to 400°C within 2 h. Mass variation was continuously recorded by means of a suspension magnetic balance, and the gas phase was analysed by mass spectrometry. Sulphur contents were also determined at intermediate temperatures by chemical analyses. Thus, mass variations due to the presence of adsorbed species or to the formation of CoMo sulphides could be distinguished. The rapid gain in mass noted at 40°C was mostly due to adsorption of H₂S over the oxidic solid, since it increased with H₂S partial pressure. At this stage, however, a small amount of the reactive oxygen was already exchanged for sulphur. Upon raising the temperature, the mass decreased due to a combination of desorption and sulphiding steps. Above 140°C, H₂S consumption was evidenced, together with water production, and the rate of sulphiding increased with the H₂S partial pressure. At 300°C, the mass variation was close to that expected for complete transformation into Co₉S₈ and MoS₂. Above 350°C, the mass further increased due to the replacement of adsorbed water by H₂S. At 400°C, an important excess mass was observed at all H₂S partial pressures. Thus, the adsorption sites on the metal sulphides are essentially saturated by H₂S species under practical conditions.     

Competitive reactions catalyzed by NiMo-containing zeolites

The rates of benzene hydrogenation and of n-heptane hydroconversion were measured simultaneously over a series of bifunctional catalysts. The catalysts were Y zeolites containing a Ni or Mo sulfide. At 280 °C, and for the more acidic catalysts, both rates appeared linearly correlated, suggesting that the hydrogenation function was limiting.     

Influence of sulfation and structure of zirconia on catalytic isomerization of n‐hexane

Two series of sulfated zirconia have been prepared by immersing amorphous or crystalline zirconia in an H₂SO₄ solution (0.25–2.5 M). They were compared with a commercial sulfated zirconium hydroxide. Activation temperature was varied between 300 and 725°C. Sulfate density varied so that the mean surface area of an individual sulfate ranged from 0.14 to 0.54 nm². Three limiting sulfate states are evidenced and characterized by TPRMS. Catalysts are tested for isomerization of nhexane at 150°C and 3 MPa. Factors influencing the activity are discussed. The data show that a highly active and selective catalyst for producing hexane isomers requires tetragonal zirconia with a sulfate occupancy of about 0.40 nm². Preparation parameters must therefore be adapted to match these constraints.     

Kinetics of sulfur model molecules competing with H2S as a tool for evaluating the HDS activities of commercial CoMo/Al2O3 catalysts

The relative-volume activities (RVAs) for real feedstocks HDS of four commercial CoMo/Al₂O₃ catalysts have been compared to the rates for thiophene and dibenzothiophene conversion. The reaction of thiophene competing with H₂S was studied in flow microreactors under a wide range of conditions: 300–400°C, overall pressure 0.1 or 3 MPa, thiophene pressure 8–125 kPa, H₂S content 0–15 mol%. The reaction of dibenzothiophene (DBT, 2 wt% in decaline) was carried out in a batch reactor at 335°C and 4 MPa.

The conversion of the two model molecules proceeds through the same mechanism with a preliminary dearomatization step followed by parallel hydrogenolysis and hydrogenation. From kinetic modeling, the global rates and the contribution of the hydrogenation and hydrogenolysis routes to HDS were determined. Under pressure, hydrogenolysis was predominant. In that case, thiophene and DBT behaved similarly and their initial relative rates did not correlate the RVA. Industrial HDS is controlled by hydrogenation as evidenced by the good correlation between RVA and the rates of dearomatization of thiophene at atmospheric pressure and hydrogenation of the product biphenyl from DBT under pressure. It is concluded that the reaction of model molecules under selected conditions can appraise rapidly industrial HDS.     

Impact of copper and cadmium on aerobic and anaerobic digestibility of sonicated sludge

The effects of the introduction of a sludge reduction process such as ultrasound on batch aerobic and anaerobic biodegradability after exposition to two metals (copper and cadmium) were investigated. The specific energy of ultrasonic treatment applied to the sludge was 200,000 kJ kg TS(-1). Ultrasonic treatment led to floc size reduction and to organic matter solubilization. Low copper (< 5 mg L(-1)) and cadmium (< 1 mg L(-1)) concentration improved aerobic biodegradability. For high metal concentration the maximal instantaneous biogas production rate q(max) inhibition by copper and cadmium was modeled by a saturation-type relationship under aerobic and anaerobic conditions. Under aerobic conditions, respiration inhibition was not affected by sonication. Cadmium inhibition (74%) was more than copper (58%). The positive effect of sonication on CO2 production was maintained after metal introduction. Under anaerobic conditions, metal introduction cancelled out the positive effect of the treatment. The sonicated sludge was 16% less sensitive to copper inhibition but 10% more sensitive to cadmium inhibition compared to non sonicated sludge.     

Investigation of CoNiMo/Al2O3 catalysts: Relationship between H2S adsorption and HDS activity

Sulfidation of trimetallic CoNiMo/Al₂O₃ catalysts was studied by thermogravimetry at 400 °C under flow and pressure conditions. Results were compared with those obtained on prepared and industrial CoMo/Al₂O₃ and NiMo/Al₂O₃ catalysts. The amount of sorbed H₂S on the sulfided solids was measured at 300 °C in the H₂S pressure range 0–3.5 MPa at constant H₂ pressure (3.8 MPa). The adsorption isotherms were simulated using a model featuring dissociated adsorption of H₂S on supported metal sulfides and bare alumina. The amount of sulfur-vacancy sites could thus be determined under conditions close to industrial practice. A relationship with activity results for thiophene HDS and benzene hydrogenation was sought for.