The role of sulfur trapped in micropores in the catalytic partial oxidation of hydrogen sulfide with oxygen

The catalytic oxidation of hydrogen sulfide into sulfur with molecular oxygen has been studied in the temperature range 130–200 °C. Active carbon, molecular sieve 13X and liquid sulfur were used as catalysts. Sulfur is adsorbed in the micropores (3 < r < 40 Å) of the catalysts. Experiments with a surface of liquid sulfur demonstrated that sulfur is a catalyst for H2S oxidation.\ud \ud This catalytic function reflects itself in the fact that H2S oxidation rate showed a maximum as a function of the amount of sulfur present in the pores of active carbon and molecular sieve 13X. The kinetics of the reaction and the activation energy are equal on catalysts of different chemical composition.\ud \ud The mechanism of the catalysis by sulfur is discussed as well as the function of traces of iron oxide, present in most catalysts

The adsorption of sulfur by microporous materials

The sorption of sulfur by the zeolites NaX (= 13X) and CaA (= 5A) and an activated charcoal prepared from sugar was investigated at temperatures between 150 and 350°C and relative sulfur pressures between 10−4 and 10−1. The adsorbate-adsorbate interaction indicated by the S-shaped isotherm for the zeolite NaX points to physical or chemical interaction of sulfur molecules in neighboring supercages. In CaA adsorbate-adsorbate interaction between sulfur species in different supercages is negligible. Below 200°C the rate of sulfur uptake by the zeolite CaA is determined by the diffusion rate of a sulfur species through the zeolitic framework. In activated charcoal a strong adsorbate-adsorbent interaction is present and part of the sulfur is chemisorbed at 350°C. The differences in the density of the adsorbed sulfur determined with three different methods indicate that even at full saturation of the micropore volume with sulfur, there is still some residual adsorption volume

Mercury chemisorption by sulfur adsorbed in porous materials

The sorption of mercury vapor by adsorbed sulfur in the zeolites CaA (= 5A) and NaX (=13X) and two types of active carbon has been measured at a temperature of 50°C. With increasing degree of micropore filling by sulfur the fraction of sulfur accessible to mercury atoms decreased for CaA and NaX. The sulfur chemisorbed on carbon (only less than 0.05 g sulfur per g) is not very active for mercury chemisorption. The mercury uptake shows a sharp maximum as a function of the amount of sorbed sulfur in the case of CaA, NaX and activated sugar charcoal. The oxidation rate of H2S with oxygen on NaX and activated sugar charcoal correlates with the capacity for mercury chemisorption, both as a function of the amount of sorbed sulfur. From the amount of sorbed mercury an estimate of the specific sulfur surface area may be given. When sulfur impregnated CaA, NaX or activated sugar charcoal are used as adsorbents for mercury traces out of gas streams, the mercury sorption capacity may be maximized by using materials with a micropore volume approximately half filled with sulfur

The mechanism of the catalytic oxidation of hydrogen sulfide *1: III. An electron spin resonance study of the sulfur catalyzed oxidation of hydrogen sulfide

ESR experiments on the oxidation of hydrogen sulfide were performed in the temperature range 20–150 °C. Alumina, active carbon and molecular sieve zeolite 13X were investigated as catalysts. For zeolite 13X it was demonstrated that the reaction is autocatalytic and that sulfur radicals are the active sites for oxygen chemisorption. The intensity of the sulfur radical ESR signal, which is related to the degree of conversion of these radicals, by oxygen, fits in with an oxidation-reduction mechanism.\ud \ud The sulfur-oxygen radical species, which appear when oxygen is admitted to sulfur radicals, are assigned to sulfur chains containing one or two oxygen atoms at the end of the chain. It is very likely that these sulfur-oxygen radicals are intermediates in the proposed mechanism. The formation of the byproduct SO2 from SxO2 · − at temperatures above 175 °C is also visible in the ESR spectrum.\ud \ud On the basis of the experiments it is concluded that in the mechanism of H2S oxidation on active carbons, carbon radicals do not play an important role

n-Heptane hydroconversion over nickel-loaded aluminum- and/or boron-containing BEA zeolites prepared by recrystallization of magadiite varieties

Phase-pure [Al]BEA and [Al,B]BEA zeolites, prepared by solid-state recrystallization of synthetic aluminum-containing magadiites and conventionally synthesized [B]BEA, were tested, after ion exchange with nickel, as bifunctional catalysts for hydroconversion of n-heptane. The reducibility of nickel ions incorporated into BEA zeolites by ion exchange was investigated by temperature-programmed reduction (TPR). The acidity of the samples was characterized with strong (pyridine (Py), ammonia (NH3)) and weak (nitrogen) bases. The adsorbed bases were studied by transmission FT-IR (Py), diffuse reflectance infrared Fourier-transform (DRIFT) spectroscopy (N2), and temperature-programmed ammonia evolution (TPAE, NH3). Over Ni/H-[B]BEA the reactants were completely converted via fast hydrogenolysis, whereas this reaction pathway plays only a negligible role in the hydroconversion over Ni/H-[Al]BEA and Ni/H-[Al,B]BEA zeolites. Boron-containing BEA zeolites were less active catalysts than the boron-free catalyst in the principal unimolecular hydroconversion reactions. However, incorporation of boron into the framework of BEA zeolite results in a considerable selectivity shift towards isomerization. Results suggest that the acid strength of bridged hydroxyls, probed with weak (N2) and strong basis (pyridine), was found to be similar in the boron-free and boron-containing BEA samples. The decrease in the isomerization rate and the increase of the apparent activation energy upon incorporation of boron may be attributed to the decrease in the heat of n-heptane adsorption

A reappraisal of the impact of dairy foods and milk fat on cardiovascular disease risk

Background This review provides a reappraisal of the potential effects of dairy foods, including dairy fats, on cardiovascular disease (CVD)/coronary heart disease (CHD) risk. Commodities and foods containing saturated fats are of particular focus as current public dietary recommendations are directed toward reducing the intake of saturated fats as a means to improve the overall health of the population. A conference of scientists from different perspectives of dietary fat and health was convened in order to consider the scientific basis for these recommendations. Aims This review and summary of the conference focus on four key areas related to the biology of dairy foods and fats and their potential impact on human health: (a) the effect of dairy foods on CVD in prospective cohort studies; (b) the impact of dairy fat on plasma lipid risk factors for CVD; (c) the effects of dairy fat on non-lipid risk factors for CVD; and (d) the role of dairy products as essential contributors of micronutrients in reference food patterns for the elderly. Conclusions Despite the contribution of dairy products to the saturated fatty acid composition of the diet, and given the diversity of dairy foods of widely differing composition, there is no clear evidence that dairy food consumption is consistently associated with a higher risk of CVD. Thus, recommendations to reduce dairy food consumption irrespective of the nature of the dairy product should be made with cautionJ. Bruce German, Robert A. Gibson, Ronald M. Krauss, Paul Nestel, Benoît Lamarche, Wija A. van Staveren, Jan M. Steijns, Lisette C. P. G. M. de Groot, Adam L. Lock and Frédéric Destaillat

Protein type, protein dose, and age modulate dietary protein digestion and phenylalanine absorption kinetics and plasma phenylalanine availability in humans

This is the final version. Available from the publisher via the DOI in this record.BACKGROUND: Dietary protein ingestion stimulates muscle protein synthesis by providing amino acids to the muscle. The magnitude and duration of the postprandial increase in muscle protein synthesis rates are largely determined by dietary protein digestion and amino acid absorption kinetics. OBJECTIVE: We assessed the impact of protein type, protein dose, and age on dietary protein digestion and amino acid absorption kinetics in vivo in humans. METHODS: We included data from 18 randomized controlled trials with a total of 602 participants [age: 53 ± 23 y; BMI (kg/m2): 24.8 ± 3.3] who consumed various quantities of intrinsically l-[1-13C]-phenylalanine-labeled whey (n = 137), casein (n = 393), or milk (n = 72) protein and received intravenous infusions of l-[ring-2H5]-phenylalanine, which allowed us to assess protein digestion and phenylalanine absorption kinetics and the postprandial release of dietary protein-derived phenylalanine into the circulation. The effect of aging on these processes was assessed in a subset of 82 young (aged 22 ± 3 y) and 83 older (aged 71 ± 5 y) individuals. RESULTS: A total of 50% ± 14% of dietary protein-derived phenylalanine appeared in the circulation over a 5-h postprandial period. Casein ingestion resulted in a smaller (45% ± 11%), whey protein ingestion in an intermediate (57% ± 10%), and milk protein ingestion in a greater (65% ± 13%) fraction of dietary protein-derived phenylalanine appearing in the circulation (P < 0.001). The postprandial availability of dietary protein-derived phenylalanine in the circulation increased with the ingestion of greater protein doses (P < 0.05). Protein digestion and phenylalanine absorption kinetics were attenuated in older when compared with young individuals, with 45% ± 10% vs. 51% ± 14% of dietary protein-derived phenylalanine appearing in the circulation, respectively (P = 0.001). CONCLUSIONS: Protein type, protein dose, and age modulate dietary protein digestion and amino acid absorption kinetics and subsequent postprandial plasma amino acid availability in vivo in humans. These trials were registered at clinicaltrials.gov as NCT00557388, NCT00936039, NCT00991523, NCT01317511, NCT01473576, NCT01576848, NCT01578590, NCT01615276, NCT01680146, NCT01820975, NCT01986842, and NCT02596542, and at http://www.trialregister.nl as NTR3638, NTR3885, NTR4060, NTR4429, and NTR4492

ChemInform Abstract: THE MECHANISM OF THE CATALYTIC OXIDATION OF HYDROGEN SULFIDE. III. AN ELECTRON SPIN RESONANCE STUDY OF THE SULFUR CATALYZED OXIDATION OF HYDROGEN SULFIDE

ESR experiments on the oxidation of hydrogen sulfide were performed in the temperature range 20–150 °C. Alumina, active carbon and molecular sieve zeolite 13X were investigated as catalysts. For zeolite 13X it was demonstrated that the reaction is autocatalytic and that sulfur radicals are the active sites for oxygen chemisorption. The intensity of the sulfur radical ESR signal, which is related to the degree of conversion of these radicals, by oxygen, fits in with an oxidation-reduction mechanism.\ud \ud The sulfur-oxygen radical species, which appear when oxygen is admitted to sulfur radicals, are assigned to sulfur chains containing one or two oxygen atoms at the end of the chain. It is very likely that these sulfur-oxygen radicals are intermediates in the proposed mechanism. The formation of the byproduct SO2 from SxO2 · − at temperatures above 175 °C is also visible in the ESR spectrum.\ud \ud On the basis of the experiments it is concluded that in the mechanism of H2S oxidation on active carbons, carbon radicals do not play an important role