Parr Reactor Research Articles

Catalytic Properties of Cu/13X Zeolite Based Catalyst in Catalytic Wet Peroxide Oxidation of Phenol

Copper bearing 13X zeolite was prepared from commercial 13X zeolite via ion-exchange with copper acetate solutions. After the incorporation of copper, Cu/13X catalyst was exposed to post synthesis thermal treatment at different temperatures. The prepared catalysts were characterized by XRD and FTIR, while the adsorption techniques were used for the measurement of the specific surface area and pore volume. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at atmospheric pressure in temperature range from 333 to 353 K. Influence of postsynthesis thermal treatment and reaction temperature on activity and stability of prepared catalysts in the catalytic wet oxidation process with hydrogen peroxide as oxidant was investigated. The experimental results showed that total degradation of phenol can be achieved under mild operating conditions at temperatures bellow 353 K. All catalysts exhibited higher activity in terms of hydrogen peroxide and phenol abatement with the increasing temperature of the reaction. The postsynthesis thermal treatment resulted in more stable catalyst with respect to stability of both catalysts’ active metal component (copper) and support, while the activity of catalysts in terms of TOC conversion remained unaltered.

ChemInform Abstract: Scalable Synthesis of Tavorite LiFeSO4F and NaFeSO4F Cathode Materials.

AbstractTavorite LiFeSO4F as a cathode material for rechargeable Li‐ion cells and the new possible Na‐ion battery material NaFeSO4F are synthesized by rapidly heating FeSO4·7H2O for 3 h at 100 °C under N2/7% H2 followed by ball‐milling with NaF or LiF, and reacting the mixture solvothermally in tetraethylene glycol (Parr reactor, 220 °C, 60 h (Li), 48 h (Na)).

Effect of Ruthenium Metal Precursors Supported on Bentonite in Hydrogenolysis Glycerol

Various ruthenium precursors (Ru= RuCl3, Ru2 = Ru(acac)3, Ru3 = Ru3(CO)12) supported on bentonite were prepared by conventional impregnation method. Their catalytic performances were evaluated in the hydrogenolysis of glycerol using autoclave Parr reactor under mild reaction conditions of 150°C, hydrogen pressure 30 bar for 7 hours. Among the studied catalyst, 5% Ru/bentonite catalyst prepared from Ru and Ru3 precursor exhibited higher activity which are 79.6% and 72.5% respectively. In contrast, Ru2/bentonite prepared from Ru(acac)3 precusor gave lowest activity (41.8%). In term of selectivity to 1,2-propanediol, Ru2 and Ru3 precusor gave higher selectivity (67.0% and 66.9%) compared to Ru precursor (50.6%). These results indicated that metal precursor plays an important role on activity and selectivity of the catalyst in hydrogenolysis reaction. The catalysts were characterized by XRD, XPS, BET, FESEM-EDX and TEM, and the reasons for the high performances of the catalyst were also discussed.

Phenolics extraction from Agave americana (L.) leaves using high-temperature, high-pressure reactor

The Agave americana plant has been largely used in traditional medicine. The setting up of efficient methods for phenolics extraction from A. americana leaves is one of great interest. With the aim of optimizing phenolics extraction from this material, the effects of temperature (from 25 to 150 °C) and extraction time (from 15 to 240 min) were investigated using a high-temperature, high-pressure (PARR) reactor, under either air or nitrogen atmosphere. Total polyphenols and flavonoids were determined, and their antioxidant activity was measured by the DPPH radical method. The use of PARR reactor for phenolics extraction proved to be more efficient compared to the conventional solid–liquid extraction at room temperature. The results of this work demonstrated that an increase in both temperature and extraction time led to a corresponding increase in the amount of phenolic compounds extracted and suggested that, after process optimization, this material could be used as an interesting alternative source of polyphenols.

Scalable Synthesis of Tavorite LiFeSO4F and NaFeSO4F Cathode Materials

Tavorite LiFeSO4F as a cathode material for rechargeable Li-ion cells and the new possible Na-ion battery material NaFeSO4F are synthesized by rapidly heating FeSO4·7H2O for 3 h at 100 °C under N2/7% H2 followed by ball-milling with NaF or LiF, and reacting the mixture solvothermally in tetraethylene glycol (Parr reactor, 220 °C, 60 h (Li), 48 h (Na)).

ChemInform Abstract: Structural, Transport, and Electrochemical Investigation of Novel AMSO4F (A: Na, Li; M: Fe, Co, Ni, Mn) Metal Fluorosulfates Prepared Using Low Temperature Synthesis Routes.

AbstractThe sodium‐based title compounds are synthesized by solid state reaction of MSO4·H2O (M: Fe, Co, Ni, Mn) and a slight excess of NaF (Parr reactor, 300 °C, 40—50 h) and ionothermally from mixtures of the same precursors and [emim][NTf2] (autoclave, 300 °C, 9 h).

ORIGINAL RESEARCH: Lignocellulose recalcitrance screening by integrated high-throughput hydrothermal pretreatment and enzymatic saccharification

We report a novel 96-well multiplate reactor system for comparative analysis of lignocellulose recalcitrance via integrated hydrothermal pretreatment and enzymatic saccharification. The system utilizes stackable nickel/gold-plated 96-well aluminum reactor plates, a clamping device fit to a standard Parr reactor, and robotics for efficient liquids and solids handling. A capacity of 20 plates allows up to 1,920 separate hydrothermal reactions per run. Direct and rapid analysis of key end-products, glucose and xylose, is facilitated by the use of glucose oxidase/peroxidase and xylose dehydrogenase-linked assays. To demonstrate efficacy, a set of 755 poplar core samples from the US Department of Energy’s BioEnergy Science Center was tested. Total sugar release ranged from 0.17 to 0.64 g/g of biomass and correlated strongly with the ratio of syringyl to guaiacyl lignins in the samples. Variance among sample replicates was sufficiently minimal to permit clear assignment of differences in recalcitrance throughout this large sample set.

Extraction of phenolics from Vitis vinifera wastes using non-conventional techniques

Polyphenols, the well known naturally occurring antioxidants, are the most abundant secondary metabolites in grape wastes. Herein we investigate several non-conventional extraction methods vs classic solid–liquid extraction (SLE) to obtain phenolic compounds from grape seeds and skins. We compared SLE, ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE) and high pressure and temperature extraction (HPTE) in term of extraction yield and antioxidant power of the extract. Solvent of choice between methanol and ethanol was the former, both for skins and seeds. Quali-quantitative analyses were performed using colorimetric and HPLC methods. The highest content in total polyphenols, o-diphenols and flavonoids, both for seeds (108.3, 47.0 mg GAE g DW −1, 47.2 mg CE g DW −1) and skins (34.2, 10.1 mg GAE g DW −1, 21.6 mg CE g DW −1) was obtained with HPTE working in a Parr reactor. While the highest antiradical power was determined in seeds extracts from MAE (78.6 μl extract μg DPPH −1). Prolonged extraction times (over 30 min) further increased the amount of total polyphenols, while progressively decreased the amount of flavonoids and the antiradical power.

Heterogeneous Supported Catalysts for Butadiene Polymerization: The Effect of Calcination Temperature and Solvent

The polymerization of butadiene was studied using heterogeneous cobalt nickel (oxide) bimetallic catalyst. The prepared catalyst was subjected to calcination at different temperatures. This treatment results in the formation of different phases with multiple oxidation states. The characterization of the catalyst was carried out by XRD, SEM, EDX, TGA, FTIR and TPR/TPD. The catalytic activity was studied for the polymerization of butadiene gas in toluene, n-hexane and ethanol in a Parr reactor system. The products obtained, were characterized by FTIR, GC/MS, 1 H and 13 C NMR spectroscopy, Laser Light Scattering (LLS) and GPC. The best activity was achieved on the catalyst sample calcined at 1173 K in ethanol solvent. The product contains aliphatic and aromatic carbonyl compounds and polybutadiene terminated by OH group. The GPC and LLS studies indicates that polydispersity of the products are in the narrow range and high molecular weight product. The study reflects that the catalytic reaction conditions, the calcinations temperatures which control the oxidation state, phase of the catalyst and stability of the catalyst are mainly responsible for the change in products selectivity.

Characterization of novolac type liquefied wood/phenol/formaldehyde (LWPF) resin

Novolac type liquefied wood/phenol/formaldehyde (LWPF) resins were synthesized from liquefied wood and formaldehyde. The average molecular weight of the LWPF resin made from the liquefied wood reacted in an atmospheric three neck flask increased with increasing P/W ratio. However, it decreased with increasing phenol/wood ratio when using a sealed Parr reactor. On average, the LWPF resin made from the liquefied wood reacted in the Parr reactor had lower molecular weight than those from the atmospheric three neck flask. The infrared spectra of the LWPF resins were similar to that of the conventional novolac resin but showed a major difference at the 1800–1600 cm-1 region. These results indicate that liquefied wood could partially substitute phenol in the novolac resin synthesis. The composites with the liquefied wood resin from the sealed Parr reactor yielded higher thickness swelling than those with the liquefied wood resin from the three neck flask likely due to the hydrophilic wood components incorporated in it and the lower cross-link density than the liquefied wood resin from the three neck flask during the resin cure process.

Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies

In order to investigate changes in substrate chemical and physical features after pretreatment, several characterizations were performed on untreated (UT) corn stover and poplar and their solids resulting pretreatments by ammonia fiber expansion (AFEX), ammonia recycled percolation (ARP), controlled pH, dilute acid, flowthrough, lime, and SO 2 technologies. In addition to measuring the chemical compositions including acetyl content, physical attributes determined were biomass crystallinity, cellulose degree of polymerization, cellulase adsorption capacity of pretreated solids and enzymatically extracted lignin, copper number, FT-IR responses, scanning electron microscopy (SEM) visualizations, and surface atomic composition by electron spectroscopy of chemical analysis (ESCA). Lime pretreatment removed the most acetyl groups from both corn stover and poplar, while AFEX removed the least. Low pH pretreatments depolymerized cellulose and enhanced biomass crystallinity much more than higher pH approaches. Lime pretreated corn stover solids and flowthrough pretreated poplar solids had the highest cellulase adsorption capacity, while dilute acid pretreated corn stover solids and controlled pH pretreated poplar solids had the least. Furthermore, enzymatically extracted AFEX lignin preparations for both corn stover and poplar had the lowest cellulase adsorption capacity. ESCA results showed that SO 2 pretreated solids had the highest surface O/C ratio for poplar, but for corn stover, the highest value was observed for dilute acid pretreatment with a Parr reactor. Although dependent on pretreatment and substrate, FT-IR data showed that along with changes in cross linking and chemical changes, pretreatments may also decrystallize cellulose and change the ratio of crystalline cellulose polymorphs (Iα/Iβ).

Catalytic Hydrogenolysis of Glycerol to Propylene Glycol over Mixed Oxides Derived from a Hydrotalcite-Type Precursor

Selective hydrogenolysis of glycerol to propylene glycol was performed using an environmentally friendly hydrotalcite-derived mixed-metal oxide catalyst. The Mg/Al, Zn/Al, Ni/Mg/Al, Ni/Co/Mg/Al, and Cu/Zn/Al mixed-metal oxide catalysts were prepared from their corresponding hydrotalcite precursors having M2+/M3+ compositions over the range of 0.5−3.0. The physicochemical properties of the catalysts were studied by X-ray diffraction (XRD), inductively coupled plasma mass spectrometry (ICP-MS), NH3 and CO2 temperature-programmed desorption (TPD), and nitrogen adsorption studies. The XRD patterns of pure hydrotalcites exhibited characteristics of hydrotalcite phases, while those of calcined hydrotalcites showed the formation of corresponding metal oxides. The ICP-MS analysis showed agreement between the calculated and actual metal compositions. The prepared catalysts were evaluated for the hydrogenolysis of glycerol to propylene glycol in a Parr reactor. The activity studies indicated a maximum glycerol conv...

Catalytic wet air oxidation of gasoline oxygenates using Rh/γ-Al 2O 3 and Rh/γ-Al 2O 3–CeO 2 catalysts

Catalytic wet air oxidation of gasoline oxygenates (ETBE and TAME) were carried out using Rh/γ-Al 2O 3, Rh/γ-Al 2O 3–CeO 2 catalysts in a Parr reactor at 100, 120 and 150 °C using oxygen as oxidant source at 10 bar of pressure. Aqueous solutions of ETBE and TAME were prepared using the quantities necessary to obtain 227 ppm. The quantity of catalyst used was 1 g/L. Cerium emphasizes the oxidative capacity of the rhodium catalysts at 100 °C explained by the formation of rhodium oxide sites (Rh 2O 3) at the surface, detected by TPR and XPS techniques. This capacity has been observed by the high CO 2 selectivity due to the support–metal interaction by the formation of Ce 4+–O 2−–M + bond which prevents the formation of carboxylic acids intermediate as acetic, the most refractory acid found.

Characterization and Activity of Cu/ZSM5 Catalysts for the Oxidation of Phenol with Hydrogen Peroxide

AbstractThe heterogeneous catalytic wet peroxide oxidation (CWPO), involving total oxidation of organic compounds to CO2 and H2O is a possible path for the treatment of toxic and bio‐refractory wastewater streams. The aim of this work was to synthesize and characterize three Cu/ZSM5 catalysts prepared by direct hydrothermal synthesis. The mass ratio of the active metal component in the zeolite ranged from 1.62–3.24 wt %. These materials were tested for CWPO of aqueous phenol in a stainless steel Parr reactor, in batch operation under mild conditions (at atmospheric pressure and a temperature of 353 K). The catalyst weight was 0.1 g dm–3 and the initial concentration of phenol and hydrogen peroxide were 0.01 mol dm–3 and 0.1 mol dm–3, respectively. The catalysts were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), AAS and ICP‐MS. Their catalytic performance was monitored in terms of phenol and total organic carbon (TOC) conversion, hydrogen peroxide decomposition, by‐product distribution and the degree of copper leached into the aqueous solution. The experimental results indicated that within 180 min, these catalysts facilitated almost complete elimination of phenol and a significant removal of chemical oxygen demand, without significant leaching of Cu ions from the zeolite. The Cu/ZSM5‐DHS3 catalyst with the highest copper loading was proven to be the best candidate. The useful fraction of hydrogen peroxide that contributed to the removal of the organic compounds quantified in terms of selectivity, S, indicated that the CWPO selectivity was always less than 100 %, which meant that there was some self‐degradation of oxidant. It was also shown that oxidation of phenol took place on the catalyst surface via a heterogeneous mechanism, and that the contribution of any homogeneous reaction mechanism was not significant.

Synthesis and cure kinetics of liquefied wood/phenol/formaldehyde resins

AbstractWood liquefaction was conducted at a 2/1 phenol/wood ratio in two different reactors: (1) an atmospheric three‐necked flask reactor and (2) a sealed Parr reactor. The liquefied wood mixture (liquefied wood, unreacted phenol, and wood residue) was further condensed with formaldehyde under acidic conditions to synthesize two novolac‐type liquefied wood/phenol/formaldehyde (LWPF) resins: LWPF1 (the atmospheric reactor) and LWPF2 (the sealed reactor). The LWPF1 resin had a higher solid content and higher molecular weight than the LWPF2 resin. The cure kinetic mechanisms of the LWPF resins were investigated with dynamic and isothermal differential scanning calorimetry (DSC). The isothermal DSC data indicated that the cure reactions of both resins followed an autocatalytic mechanism. The activation energies of the liquefied wood resins were close to that of a reported lignin–phenol–formaldehyde resin but were higher than that of a typical phenol formaldehyde resin. The two liquefied wood resins followed similar cure kinetics; however, the LWPF1 resin had a higher activation energy for rate constant k1 and a lower activation energy for rate constant k2 than LWPF2. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

A fast and simple methodology for determination of yttrium as an inert marker in digestibility studies

The need to develop a fast, simple and low cost methodology for the determination of yttrium in fish diets and faeces using a microwave digestion system and atomic absorption spectrometry with flame atomization analysis was the main aim of this study. The final methodology consisted in the digestion of approximately 300mg of dry fish diet or 100mg of dry fish faeces in teflon vessels using Parr reactor bombs, at high pressure, in a domestic microwave system with nitric acid solution. After digestion, 330μl of a 120mg potassium nitrate/ml solution was added to each solution. Yttrium was determined using a calibration with aqueous standards. Analytical difficulties and problems encountered during the optimizations were overcome and the application of the final methodology to the fish diets and faeces samples was carried out with suitable results.

Matrix importance in animal material pre-treatment for metal determination

A relatively cheap and accessible way to analyze difficult samples without loss of analyte was optimized for determination of Cd, Cr, Cu, Hg, Ni, Pb, V and Zn in animal material. Reference materials with suitable matrix were used: Dorm-2 (Dogfish Muscle), Tort-2 (Lobster Hepatopancreas), and SRM 2976 (Mussel Tissue). The analytical procedure included digestion of the sample in Parr reactor bombs combined with a commercial microwave oven and metals analysis by atomic absorption spectrometry. A weak digestion procedure was optimized to prevent metal losses: a two-step digestion with an aqueous solution of HNO 3, each step carried at a microwave power of 340 W during 4 min. With the optimized procedure, metals concentrations in all reference materials matched certified ones (for a 95% level of confidence) with the exception of Cd in Tort-2 and Hg in SRM 2976. The present work reinforces the need to use matrix-matched reference materials and that any digestion protocol needs to be modified to maximize recoveries.

Kinetics and Fluid Dynamics for Oil Residue Hydroconversion in Commercial Software

The current work is a computational simulation, with the geometry of the Parr reactor series 4581, of a multiphase system with two fluids (hydrocarbon and hydrogen) and two domains (tank and impeller) for the kinetics of residue catalytic hydrocracking. The fluid dynamics modeling is based on the SPH process and the fundamental equations of mass balance and momentum quantities in an isothermal system. The turbulence phenomena are considered through the k-? model for the hydrocarbon and ``disperse phase zero equation" for the hydrogen. The chemical reactions are modeled by the means of a reactional net based on the pseudo components concept, with their loads and products separated according to the commercial cuts, schematized with six parallel reactions, three thermal and three catalytic, with pseudo-first order reaction rates. The domains are composed of hydrocarbon as a general fluid (a mixture of pseudo components + catalyst = ``slurry phase") and the hydrogen as an ideal gas.

Investigation of the catalytic wet peroxide oxidation of phenol over different types of Cu/ZSM-5 catalyst

In this work oxidation of phenol with hydrogen peroxide on Cu/ZSM-5 catalysts was studied. The catalysts samples were prepared by two different methods: by ionic exchange from the protonic form of commercial ZSM-5 zeolite, and by direct hydrothermal synthesis. Characterization of the catalysts extends to X-ray diffraction (XRD), while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and the temperature range from 50 to 80 °C. The mass ratio of the active metal component on the zeolite was in the range of 1.62–3.24 wt.%. for catalyst prepared by direct hydrothermal synthesis and 2.23–3.52 wt.% for catalyst prepared by ion exchange method. The initial concentration of phenol and hydrogen peroxide was 0.01 and 0.1 mol dm −3, respectively. The influence of different methods of Cu/ZSM-5 preparation on their catalytic performance was monitored in terms of phenol conversion and degree of metal leached into aqueous solution.

Reactions, characterization and uptake of ammoxidized kraft lignin labeled with 15N

Ammoxidation of kraft lignin was carried out in a Parr reactor using 15NH 3 as the main nitrogen source. Reaction parameters were set up until a total nitrogen content of ≈13 wt.% in lignin was achieved, in accordance with conditions of previous studies. Analytical tools such as FTIR, Py-GC/MS, and solid state NMR were used in this research. The nature of nitrogen bondings is discussed. The incorporation of the 15N from ammoxidized lignin was followed in pumpkins ( Zucchini cucurbita pepo L.) by means of 15N emission spectroscopy.