THIS RESEARCH STUDIES THE BIODEGRADATION OF SUNFLOWER-TYPE VEGETATIVE OIL IN TWO PROPOSED ACTIVATED SLUDGE SYSTEMS, THE FIRST ONE TO BIOLOGICALLY TREAT AN INFLUENT CONTAINING ONLY VEGETATIVE OIL AND THE SECOND ONE TO TREAT A MIXTURE OF VEGETABLE OIL PLUS SACCHAROSE. THE PURPOSE OF THESE ANALYSES IS TO EVALUATE THE DIFFERENTIAL IMPACT CAUSED BY THE SOLUBLE SUBSTRATE SACCHAROSE ON THE REMOVAL OF VEGETATIVE OIL. VEGETATIVE OIL BIODEGRADATION IN BOTH SYSTEMS WAS STUDIED AND QUANTIFIED VIA INTEGRAL MASS BALANCE, AND RELEVANT OPERATING PARAMETERS WERE MONITORED. THIS EXPERIMENTATION BASED ON THE MASS BALANCE ESTIMATION OF BIODEGRADED VEGETATIVE OIL SERVES AS A REFERENCE TO UNDERSTAND THE EFFECT OF SOLUBLE SUBSTRATES PRESENT IN MIXED WASTEWATER ON OIL BIODEGRADATION. INFORMATION WAS GENERATED ON THE PERFORMANCE OF THE TWO ACTIVATED SLUDGE TREATMENT SYSTEMS. BOTH INFLUENTS WERE PRE-STIRRED BEFORE THEY ENTERED THE BENCH-SCALE ACTIVATED SLUDGE PLANTS. THE WORKING RANGE FOR SUNFLOWER OIL CONCENTRATION WAS 120 TO 520 MG/L FOR THE INFLUENT WITH SUNFLOWER OIL AND 180 TO 750 MG/L FOR THE INFLUENT WITH SUNFLOWER OIL AND SACCHAROSE. BIODEGRADATION WAS IN THE ORDER OF 56 TO 72% AND 47 TO 67%, RESPECTIVELY. THE REMOVAL OF SUNFLOWER OIL IN BIODEGRADATION AND FLOTATION WAS IN THE ORDER OF 90% IN BOTH SCENARIOS.

CATALYTIC AMINATION OF CYCLOHEXANONE WITH ANILINE IS A SUSTAINABLE METHOD FOR PRODUCING SECONDARY AMINES. IN THIS PAPER, THE FULL CHARACTERIZATION OF THE CATALYST (RH/C) IS REPORTED. MOREOVER, A REACTION PATHWAY DESCRIBING THE CATALYTIC CYCLE HAS BEEN INCLUDED AND VALIDATED WITH EXPERIMENTAL OBSERVATIONS INTEGRATED INTO DELPLOT ANALYSIS. FINALLY, A KINETIC MODEL BASED ON LANGMUIR-HINSHELWOOD FORMALISM WAS ELUCIDATED AND VALIDATED. BIOMASS-BASED AMINES HAVE RECEIVED A LOT OF ATTENTION DUE TO THEIR SUSTAINABILITY AND CARBON ECONOMY. HEREIN, THE ROLES OF THE METAL SITES (RH0 OR PD0) AND OPERATING CONDITIONS ON THE KINETICS AND REACTION PATHWAYS OF THE HETEROGENEOUS CATALYTIC AMINATION OF CYCLOHEXANONE WITH ANILINE HAVE BEEN DISCUSSED. RH/C PROVIDES SECONDARY AMINES WITH REMARKABLE SELECTIVITY TOWARD THE HYDROGENATION PRODUCT (?SI=72?%). THE HYDROGENATION RATE OVER RH0 IS 1.5-FOLD HIGHER THAN THAT OBSERVED OVER PD0, WHILE ITS DEHYDROGENATION CAPACITY DIMINISHED (RD_RH ¡=0.74?H?1 AND RD_PD=1.32?H?1). THIS DIFFERENCE IN THE HYDROGENATION/DEHYDROGENATION PERFORMANCE ALLOWS CONTROL OVER THE SELECTIVITY VIA DISPROPORTIONATION OF AN IMINE INTERMEDIATE. THE KINETIC OBSERVATIONS CAN BE REPRESENTED USING THE LANGMUIR-HINSHELWOOD MODEL, INDICATING THAT THE FORMATION OF THE AMINAL INTERMEDIATE IS THE RATE-LIMITING STEP. THE APPARENT ACTIVATION ENERGY FOR THIS STEP ON RH/C (55?KJ/MOL) WAS HIGHER THAN THAT PREVIOUSLY REPORTED FOR PD/C (48?KJ/MOL).

THE VALIDATION OF PROTOCOLS FOR CARRYING OUT THE EXPERIMENTAL ANALYSIS OF AMINATION REACTIONS IS OF PARAMOUNT IMPORTANCE TO ENHANCE THE SCIENTIFIC KNOWLEDGE AND REPRODUCIBILITY OF RESULTS. ACCORDINGLY, IN THE PRESENT PAPER, A PROTOCOL HAS BEEN PROPOSED FOR THE STUDY OF THE AMINATION OF CYCLOHEXANONE-TO-SECONDARY AMINES (DIPHENYLAMINE AND N-CYCLOHEXYLANILINE) OVER HETEROGENEOUS CATALYSTS. THE RESULTS OF ACTIVITY AND SELECTIVITY, AND THE ELUCIDATION OF A PLAUSIBLE REACTION PATHWAY WERE DESCRIBED IN A PARENT PAPER. THEREFORE, THE PURPOSE OF THIS DOCUMENT IS TO INFORM ABOUT THE DETAILS OF THE EXPERIMENTAL SETUPS, THE METHODS, AND THE ANALYTICAL TECHNIQUES TO IDENTIFY AND QUANTIFY THE REACTION PRODUCTS. FINALLY, SOME PRACTICAL AND SAFETY CONSIDERATIONS ARE ALSO INCLUDED. ? ONE-POT CATALYTIC AMINATION OF CYCLOHEXANONE WITH ANILINE WAS PERFORMED EFFICIENTLY IN LIQUID PHASE ON PD/C. ? STIRRING, HE ATMOSPHERE AND TEMPERATURE CONTROL WERE CRITICAL TO ACHIEVE REPRODUCIBLE ACTIVITY RESULTS. ? ULTRA-HIGH PERFORMANCE LIQUID CHROMATOGRAPHY ALLOWS IDENTIFYING PRODUCTS AND REACTION INTERMEDIATES, WHILE NONANE PERFORMED WELL AS INTERNAL STANDARD FOR GC-FID QUANTIFICATION.

THE LIQUID PHASE AMINATION OF THE CYCLOHEXANONE (CYO) WITH ANILINE (PHNH2) WAS STUDIED ON A PD/C CATALYST USING NACO2H AS A H-DONOR. CATALYTIC TESTS WERE PERFORMED IN BATCH REACTORS BY VARYING REACTANT CONCENTRATIONS (0, 0.1, 0.2 AND 0.4 MOL/L), THE TEMPERATURE (80?160 °C) AND H2-EQUIVALENTS AVAILABILITY (0, 2 AND 4 H2-EQUIVALENTS WITH RESPECT TO CYO). THE RESULTS INDICATE THAT, THE USE OF NACO2H BARELY AFFECT THE REACTIVITY (MEASURED AS INITIAL REACTION RATE) WHILE IT DOES INFLUENCE THE SELECTIVITY TO SECONDARY AMINES. THIS EFFECT WAS ASCRIBED TO THE LIMITED EFFECTIVITY OF THE H2 TRANSFER, WHICH WAS CONTROLLED BY THE WATER FORMED AFTER THE CONDENSATION OF THE CYO WITH THE PHNH2, HYDROGEN SOLUBILITY IN TOLUENE, AND THE MASS TRANSFER FROM THE LIQUID TO THE CATALYST SURFACE. THE EXPERIMENTAL OBSERVATIONS WERE CONSISTENT WITH A MULTI-STEP MECHANISM CONSISTING IN: A FIRST STEP OF CONDENSATION OF THE KETONE AND THE AMINE TO FORM AN IMINE, FOLLOWED BY THE DISPROPORTIONATION OF THE IMINE INTO SECONDARY AMINES. THE KINETIC MEASUREMENTS AT INITIAL RATE CONDITIONS WERE WELL INTERPRETED BY A LANGMUIR HINSHELWOOD (L-H) KINETIC MODEL, WHICH SUGGEST THAT THE SURFACE REACTION TO FORM THE INTERMEDIARY IMINE IS THE RATE LIMITING STEP (R.L.S).

THE HETEROGENEOUSLY CATALYZED REDUCTIVE AMINATION OF PHENOLICS FROM LIGNIN IS CONSIDERED AN ATTRACTIVE SUSTAINABLE ROUTE FOR THE SYNTHESIS OF PRIMARY OR HIGH-ORDER AROMATIC AND ALIPHATIC AMINES. HERE, THE REDUCTIVE AMINATION OF PHENOL WITH CYCLOHEXYLAMINE WAS STUDIED, AND INSIGHTS INTO THE ROLE OF THE CATALYST SUPPORT, METAL NANOPARTICLE SIZES, AND ACIDIC PROPERTIES WERE PROVIDED. BULK AND SURFACE CHARACTERIZATION, IR EXPERIMENTS, AND KINETIC MEASUREMENTS WERE PERFORMED, AND THEIR RESULTS WERE CORRELATED WITH THE CATALYTIC PERFORMANCE AND THE CONTENT OF LEWIS ACID SITES (PD/AL2O3 > PD/C > PD/SIO2). THE LEWIS ACID SITES IN THE SUPPORT AND THOSE FORMED BY H2 SPILLOVER ASSISTED PHENOL HYDROGENATION AND C?N BOND ACTIVATION, ENHANCING THE FORMATION OF SECONDARY AMINES (SELECTIVITY >90%). THE PD COORDINATION IN THE PARTICLES STRONGLY AFFECTED THE CATALYTIC ACTIVITY, INDICATING THAT PHENOL AMINATION IS A STRUCTURE-SENSITIVE REACTION. THE TURNOVER FREQUENCY VS. DISPERSION PROFILES COMBINED WITH THE SITE DISTRIBUTIONS IN THE PD PARTICLES (EDGE, CORNER, AND TERRACES) INDICATE THAT LOW-COORDINATION SITES FAVOR PHENOL AMINATION, WHICH WAS CONFIRMED VIA DIFFUSE REFLECTANCE INFRARED SPECTROSCOPY WITH FOURIER TRANSFORM AND HIGH-RESOLUTION TRANSMISSION ELECTRON MICROSCOPY. THIS STUDY COULD CONTRIBUTE TO THE UPCYCLING OF FRESH AND RECYCLED LIGNIN FRACTIONS TO PRODUCE AROMATIC AND ALIPHATIC AMINES.

CATALYTIC PYROLYSIS HAS BEEN USED TO UPGRADING THE QUALITY OF PYROLYTIC LIQUIDS. HEREIN, WE REPORT A COMPREHENSIVE STUDY ON THE CATALYTIC PYROLYSIS OF WASTE TIRES USING NI/SIO2 AS CATALYSTS. THE ANALYSES WERE CARRIED OUT BY COMBINING THERMOGRAVIMETRY (TGA), TGA INTERFACED TO A FOURIER TRANSFORM INFRARED SPECTROMETER (TGA?FTIR), AND PYROLYSIS COUPLED TO GAS CHROMATOGRAPHY/MASS SPECTROMETER (PY?GC/MS) TECHNIQUES. DURING WASTE TIRE DECOMPOSITION, THE MAIN FUNCTIONAL GROUPS DETECTED IN THE FTIR WERE ALKENES, AROMATICS, AND HETEROATOMS-CONTAINING GROUPS SUCH AS NITROGEN, SULFUR, AND OXYGEN. MEANWHILE, BY PY?GC/MS WERE IDENTIFIED MAINLY D,L-LIMONENE, ISOPRENE, BENZENE, TOLUENE, XYLENES (BTX), AND P-CYMENE. THE PY?GC/MS EXPERIMENTS AT THREE DIFFERENT TEMPERATURES (350, 400, AND 450 °C) SUGGESTED AN EFFECT OF THE CATALYST ON PRODUCT DISTRIBUTION. THE NI CATALYST PROMOTED CYCLIZATION REACTIONS AND SUBSEQUENTLY AROMATIZATION, LEADING TO AN IMPROVED VAPORS COMPOSITION. THE USE OF ISO-CONVERSIONAL KINETIC MODELS ALONG WITH MASTER PLOTS ALLOWS PROPOSING A MULTIPLE-STEP REACTION MECHANISM, WHICH WAS WELL DESCRIBED BY THE AVRAMI?EROFEEV, RANDOM SCISSION, AND TRUNCATED SESTAK?BERGGREN MODELS. THE VALUES OF ACTIVATION ENERGIES SHOW DIFFERENCES FOR THE CATALYZED AND UNCATALYZED PYROLYSIS (111.0 KJ MOL?1 AND 168.4 KJ MOL?1), VALIDATING THE EFFECTIVITY OF NI/SIO2. FINALLY, THE THERMAL BIOT (>?1) AND PYI AND PYII NUMBERS (10?3?