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Lauriol-Garbey P.,CNRS Research on Catalysis and Environment in Lyon | Millet J.M.M.,CNRS Research on Catalysis and Environment in Lyon | Loridant S.,CNRS Research on Catalysis and Environment in Lyon | Bellire-Baca V.,Rhodia | Rey P.,Adisseo
Journal of Catalysis | Year: 2011

Zirconium and niobium mixed oxides have been shown to be selective catalysts for dehydration of glycerol to acrolein, at 300 °C in the presence of water. The catalysts exhibit a selectivity to acrolein of approximately 72%, at nearly total glycerol conversion. More selective catalysts have been designed for this reaction, but whereas all of these are almost completely deactivated after only 24 h, ZrNbO catalysts still exhibit 82% conversion efficiency after 177 h on stream, its acrolein selectivity remaining unimpaired. Catalysts have been characterized by various techniques, showing that active and selective sites are weak or moderately acid Brønsted sites, whose presence is related to that of polymeric niobium oxide species in interaction with the zirconia support. The key stability of the catalysts has been attributed to the neutralization of Lewis acid of uncovered zirconia, which are unselective coke initiator sites. © 2011 Elsevier Inc. All rights reserved. Source


Lauriol-Garbey P.,CNRS Research on Catalysis and Environment in Lyon | Postole G.,CNRS Research on Catalysis and Environment in Lyon | Loridant S.,CNRS Research on Catalysis and Environment in Lyon | Auroux A.,CNRS Research on Catalysis and Environment in Lyon | And 3 more authors.
Applied Catalysis B: Environmental | Year: 2011

The acid-base properties of fresh and used niobium-zirconium mixed oxide catalysts, used for the dehydration of glycerol to acrolein, have been characterized by various techniques. These techniques include ammonia thermo-programmed desorption (TPD), infrared spectroscopy of absorbed pyridine, and adsorption microcalorimetry of ammonia and sulfur dioxide. Relationships between the catalytic properties and the acid-base properties of fresh catalysts have been investigated. The most efficient catalysts were shown to be those for which the zirconia support had a better niobium oxide species covering, but no specific relationship could be established between the acid-base, and the selectivity to acrolein. Characterization of the used catalysts showed that the acidic properties of the catalysts had changed considerably with the time spent on stream. No further strong acid sites, and only weak or very weak acid sites were detected. A linear relationship between the total quantity of remaining acidic sites and the rate of glycerol conversion was determined, taking into account an intrinsic activity of the stronger sites, which is more than ten times that of the weaker ones. The deactivation of the catalysts as a function of time on stream has been related to the formation of cyclic molecules, produced by the reaction of acrolein with by-products resulting from the decomposition of hydroxyacetone and also possibly acrolein and glycerol. © 2011. Source


Osorio J.S.,Urbana University | Ji P.,Urbana University | Drackley J.K.,Urbana University | Luchini D.,Adisseo | Loor J.J.,Urbana University
Journal of Dairy Science | Year: 2013

The onset of lactation in dairy cows is characterized by severe negative energy and protein balance. Methionine availability during this time for milk production, hepatic lipid metabolism, and immune function may be limiting. Supplementing Met to peripartal diets with adequate Lys in metabolizable protein (MP) to fine-tune the Lys:Met ratio may be beneficial. Fifty-six multiparous Holstein cows were fed the same basal diet from 50 d before expected calving to 30 d in milk. From -50 to -21 d before expected calving, all cows received the same diet [1.24 Mcal/kg of dry matter (DM), 10.3% rumen-degradable protein, and 4% rumen-undegradable protein] with no Met supplementation. From -21 d to expected calving, the cows received diets (1.54 Mcal/kg of DM, 10% rumen-degradable protein, and 5.1% rumen-undegradable protein) with no added Met (control, CON; n = 14), CON plus MetaSmart (MS; Adisseo Inc., Antony, France; n = 12), or CON plus Smartamine M (SM; Adisseo Inc.; n = 12). From calving through 30 d in milk, the cows received the same postpartum diet (1.75 Mcal/kg of DM and 17.5% CP; CON), or the CON plus MS or CON plus SM. The Met supplements were adjusted daily and top-dressed over the total mixed ration at a rate of 0.19 or 0.07% (DM) of feed for MS or SM. Liver tissue was collected on -10, 7, and 21 d, and blood samples more frequently, from -21 through 21 d. Data were analyzed using the MIXED procedure of SAS (SAS Institute Inc., Cary, NC) with the preplanned contrasts CON versus SM + MS and SM versus MS. No differences in prepartal DM intake (DMI) or body condition score were observed. After calving, body condition score was lower (2.6 vs. 2.8), whereas DMI was greater (15.4 vs. 13.3. kg/d) for Met-supplemented cows. Postpartal diet × time interactions were observed for milk fat percentage, milk fat yield, energy-corrected milk:DMI ratio, and energy balance. These were mainly due to changes among time points across all treatments. Cows supplemented with either Met source increased milk yield, milk protein percentage, energy-corrected milk, and milk fat yield by 3.4. kg/d, 0.18% units, 3.9. kg/d, and 0.18. kg/d, respectively. Those responses were associated with greater postpartum concentration of growth hormone but not insulin-like growth factor 1. There was a diet × time effect for nonesterified fatty acid concentration due to greater values on d 7 for MS; however, liver concentration of triacylglycerol was not affected by diet or diet × time but increased postpartum. Blood neutrophil phagocytosis at 21 d was greater with Met supplementation, suggesting better immune function. Supplemental MS or SM resulted in a tendency for lower incidence of ketosis postpartum. Although supplemental MS or SM did not decrease liver triacylglycerol, it improved milk production-related traits by enhancing voluntary DMI. © 2013 American Dairy Science Association. Source


Osorio J.S.,Urbana University | Trevisi E.,Catholic University of the Sacred Heart | Ji P.,Urbana University | Drackley J.K.,Urbana University | And 3 more authors.
Journal of Dairy Science | Year: 2014

The peripartal dairy cow experiences a state of reduced liver function coupled with increased inflammation and oxidative stress. This study evaluated the effect of supplementing basal diets with rumen-protected Met in the form of MetaSmart (MS) or Smartamine M (SM) (both from Adisseo Inc., Antony, France) during the peripartal period on blood and hepatic biomarkers of liver function, inflammation, and oxidative stress. Thirty-seven multiparous Holstein cows were fed the same basal diet from -50 to -21 d relative to expected calving [1.24. Mcal/kg of dry matter (DM); no Met supplementation]. From -21 d to calving, the cows received diets (1.54. Mcal/kg of DM) with no added Met (control, CON; n. =. 13), CON plus MS (n. =. 11), or CON plus SM (n. =. 13). From calving through 30 d in milk (DIM), the cows received the same postpartal diet (1.75. Mcal/kg of DM; CON), or CON plus MS or CON plus SM. Liver and blood samples were harvested at various time points from -21 to 21 d relative to calving. Preplanned contrasts of CON versus SM + MS during prepartum (-21 and -10 d before calving) and postpartum (7, 14, and 21 d after calving) responses were evaluated. Cows fed MS or SM compared with CON had lower overall concentrations of plasma ceruloplasmin and serum amyloid A (SAA). Compared with CON, Met-supplemented cows had greater overall plasma oxygen radical absorbance capacity. Liver concentrations of glutathione and carnitine also were greater overall with Met supplementation. Milk choline and liver phosphatidylcholine were lower overall in cows fed Met compared with controls. Liver tissue choline concentrations did not differ. Data indicate that supplemental Met enhanced de novo glutathione and carnitine synthesis in liver and, thus, increased antioxidant and β-oxidation capacity. The greater decrease of IL-6 after calving coupled with lower ceruloplasmin and SAA in Met-supplemented cows indicated a reduction in proinflammatory signaling within liver. The lower hepatic phosphatidylcholine in Met-supplemented cows might have been associated with greater assembly or export of very low density lipoproteins. Overall, biomarker analyses in blood and tissue indicate that the beneficial effect of feeding SM and MS on postpartal cow performance is due in part to a better immunometabolic status. © 2014 American Dairy Science Association. Source

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