Nitrogen as a Probe Molecule for the IR Studies of the Heterogeneity of OH Groups in Zeolites

One of the methods of IR studies of the heterogeneity of Si–OH–Al groups in zeolites is the investigation of the frequency shift of the band of free OH bands restored upon the adsorption of ammonia and subsequent desorption at increasing temperatures. We extended this method by following the shift of the band of the OH group interacting by hydrogen bonding with nitrogen. The advantage of nitrogen, compared with CO, which has been commonly used as a probe molecule in studies on hydrogen bonding, is that for nitrogen the frequency shift is smaller than for CO and therefore there is no overlapping of shifted OH band with the bands of ammonium ions. For zeolites NaHY, HMFI, and HBEA, the frequency shift of IR bands of both free and hydrogen-bonded Si–OH–Al with the increase of ammonia desorption temperature evidences the heterogeneity of these hydroxyls. On the other hand, in zeolite HFAU of Si/Al = 31, Si–OH–Al were found to be homogeneous. Heterogeneity of OH groups may be explained both by the presence of Si–OH–Al of various number of Al near the bridge and of Si–OH–Al of various geometry.

Rapid Ammonia Carriers for SCR Systems Using MOFs [M2(adc)2(dabco)] (M = Co, Ni, Cu, Zn)

Ammonia is one of the most common reductants for the automotive selective catalytic reduction (SCR) system owing to its high NO2 reduction (deNOx) efficiency. However, ammonia carriers for the SCR system have sluggishly evolved to achieve rapid ammonia dosing. In this study, the MOFs [M2(adc)2(dabco)] (M = Co, Ni, Cu, Zn) were synthesized and characterized as ammonia carriers. Among the four obtained MOFs, Ni2(adc)2(dabco) possessed the highest surface area, 772 m2/g, highest ammonia uptake capacity, 12.1 mmol/g, and stable cyclic adsorption-desorption performance. All the obtained MOFs demonstrated physisorption of ammonia and rapid kinetics of ammonia adsorption and desorption. Compared with halide ammonia carrier MgCl2, the obtained MOFs showed four times faster adsorption kinetics to reach 90% of the ammonia uptake capacity. For the ammonia desorption, the Ni2(adc)2(dabco) provided 6 mmol/g ammonia dosing when temperature reached 125 °C in the first 10 min, which was six times of the ammonia dosing from Mg(NH3)6Cl2. The results offer a solution to shorten the buffering time for ammonia dosing in the SCR system.

Studies on the Binary MgO/SiO2 Mixed Oxide Catalysts for the Conversion of Ethanol to 1,3-Butadiene

The demand for 1,3-butadiene, one of the most important raw materials in the rubber industry, is constantly increasing. The Lebedev process is a classical method of producing 1,3-butadiene from ethanol, which is to be optimized with regard to the mixed oxide catalysts used. In this work, the binary MgO/SiO2 solid system was tested with regard to its optimum chemical composition for the catalytic conversion of ethanol to 1,3-butadiene. Furthermore, novel mesoporous mixed oxides were prepared to investigate their textural, structural, and surface chemical properties as well as the catalytic activity. Nitrogen physisorption, scanning electron microscopy (SEM), and temperature-programmed ammonia desorption (NH3-TPD) measurements were carried out and evaluated. It was shown that the optimum yield of 1,3-butadiene is achieved by using MgO/SiO2 mixed oxide catalysts with 85–95 mol% MgO and not, as suggested by Lebedev, with 75 mol% MgO. The NH3-TPD measurements revealed that the maximum acid-site density is achieved with an equimolar up to magnesium-rich composition. During the synthesis of binary MgO/SiO2 solid systems based on mesoporous MgO, a thermally stable and ordered structure was formed in the autoclave, depending on the carbonate used and on the duration of the treatment.

KESETIMBANGAN PROSES DESORPSI AMONIA DARI ARANG AKTIF HASIL PIROLISIS LIMBAH BIOMASSA

Ammonia which is bound to the adsorbent can interfere adsorption process, so that release the compound can be done by desorption process. This research intends to know appropriate equilibrium models to determine maximum capacity of active carbon for desorption ammonia. The method which used in desorption process are Langmuir and Freundlich isotherm models. The research was performed with variation of active carbon mass and variation of contact time. The concentration of ammonia on the desorption process was determined using spectrophotometer at λ 420 nm. The experiment result showed that the more the active carbon dosage is used, the more the concentration of ammonia is increased. Optimum contact time during 7 hours with desorption percentage 94-96%. This research of ammonia desorption by active carbon followed the Langmuir equilibrium model R2 0.954 and Freundlich equilibrium model R2 0.952. The equilibrium equation is used Langmuir equation y = -0.015x + 3.185, maximum desorption capacity is 66.67 mg/g.

Microwave-Assisted Furfural Production Using Hectorites and Fluorohectorites as Catalysts

It has previously been reported that the use of microwave heating, together with the presence of co-solvents, improves the efficiency of furfural production from biomass. Solid acid catalysts can be a good alternative to mineral acids, since they can prevent corrosion and can be reused. However, the formation of humines should be minimized. Several delaminated and fluorinated hectorites, with different types and strengths of acid sites, were synthesized and tested as catalysts for the production of furfural from commercial xylose and from an acid biomass extract of almond shells. A new methodology was developed to prepare crystalline fluorohectorite at 800 °C in just 3 h. The presence of F significantly increased the acidity strength in the protonated fluorohectorite (H-FH) taking into account its high ammonia desorption temperature (721 °C). Additionally, this sample had fourteen times higher total acidity by m2 than the reference H-βeta acid catalyst. H-FH was the most efficient catalyst at short reaction times (1 h) for the transformation of xylose to furfural under microwaves using toluene as co-solvent, regardless of whether the xylose was commercial (20% furfural yield) or an extract of almond shells (60% furfural yield). However, the acidity of the extract affected the fluorohectorite structure and composition.

Catalyst/Feedstock Ratio Effect on FCC Using Different Catalysts Samples

The present study is a follow-up to a recent authors contribution which describes the effect of the C/O (catalyst/oil) ratio on catalytic cracking activity and catalyst deactivation. This study, while valuable, was limited to one fluidized catalytic cracking (FCC) catalyst. The aim of the present study is to consider the C/O effect using three FCC catalysts with different activities and acidities. Catalysts were characterized in terms of crystallinity, total acidity, specific surface Area (SSA), temperature programmed ammonia desorption (NH3-TPD), and pyridine chemisorption. 1,3,5-TIPB (1,3,5-tri-isopropyl benzene) catalytic cracking runs were carried out in a bench-scale mini-fluidized batch unit CREC (chemical reactor engineering centre) riser simulator. All data were taken at 550 °C with a contact time of 7 s. Every experiment involved 0.2 g of 1,3,5-TIPB with the amount of catalyst changing in the 0.12–1 g range. The resulting 0.6–5 g oil/g cat ratios showed a consistent 1,3,5-TIPB conversion increasing first, then stabilizing, and finally decreasing modestly. On the other hand, coke formation and undesirable benzene selectivity always rose. Thus, the reported results show that catalyst density affects both catalyst coking and deactivation, displaying an optimum C/O ratio, achieving maximum hydrocarbon conversions in FCC units.

Ammonia desorption from fly ash

The main source of ammonia in ash are residues from an unreacted NH3 from the denitrification process, either from SCR or SNCR systems. The paper discusses the standards of NH3 content in fly ash and presents the most commonly used methods of removing excess ammonia from fly ash. In the next part of the work the results of laboratory tests on NH3 desorption are presented. Desorption was performed on samples of fly ash taken from the electrostatic precipitator of real PC boiler. Removal of NH3 from the ash was carried out in a heating chamber at 130°C and 150°C and detected by an analyser equipped with a NDIR sensor. Additionally, at the temperature of 130°C, the NDIR and analytical methods were compared (in accordance with the BN-750541-05 procedure) and the measurement uncertainty of both methods was estimated.

Production, Physicochemical and Catalytic Properties of Gallium-Containing Zeolite Catalysts

<p>Crystalline galloalumino- and gallosilicates with pentasil structure were synthesised under hydrother-mal conditions. The influence of gallium concentration and binder amount both on physicochemical and catalytic properties of a zeolite in the process of C₂-C₄ light alkanes aromatization and on catalyst deacti-vation due to carbidization has been studied. Acidic properties of gallium-containing pentasils with differ-ent composition were studied using the method of thermoprogrammed ammonia desorption. The forma-tion of strong aproton acidic sites whose composition includes gallium ions was found. It has been shown that isomorphic aluminium replacement by gallium in the pentasil lattice leads to a significant increase in aromatizing activity and period of stable catalyst operation. A decrease in intensity of coking and the formation of less condensed coke deposits with a wide distribution by the structure are observed with the increase in gallium concentration. The introduction of a binder to galloaluminosilicate results in a signifi-cant increase in mechanical strength of a catalyst. It was established that the most efficient catalyst of the above process is a zeolite containing 2.2% of gallium oxide and 1.3% of aluminium oxide and mixed with 20% of the pseudobeumite. The selectivity of the formation of aromatic hydrocarbons reaches 55-60%, the period of stable operation exceeds 350 h. In accordance with the data obtained suggested are the principles of the selection of efficient catalysts of light alkanes aromatization and optimum conditions of the process.</p>

Modification, Characterization, and Catalytic Application of Mesolite for One Pot Synthesis of 3-Methyl-4-arylmethylene-isoxazol-5(4H)-ones

<p>Natural mesolite type zeolite was collected, modified by sulphuric acid treatment and characterized by using Powder-X ray diffraction, Scanning electron microscopy and Energy dispersive spectroscopy, Fourier transform infrared spectroscopy. Temperature programmed ammonia desorption, Brunauer-Emmer-Teller surface area analysis. Modified dealuminated mesolite shows an efficient catalytic activity for one pot synthesis of 3-methyl-4-arylmethylene-isoxazol-5(4H)-ones derivatives, via one pot three component condensation of benzaldehyde, ethylacetoacetate and hydroxylamine hydrochloride. Present method offers several advantages over the reported methods like a simple and inexpensive modification of catalyst, mild reaction condition, easy separation of catalyst, simple work-up procedure, nonchromatographic isolation and purification desired product and excellent yield. Furthermore, catalyst could be reused without significant loose in activity. Copyright © 2017 BCREC GROUP. All rights reserved</p><p><em>Received: 25^th August 2016; Revised: 10^th October 2016; Accepted: 17^th October 2016</em></p><strong>How to Cite:</strong> Pawar, G.T., Gadekar, S.P., Arbad, B.R., Lande, M.K. (2017). Modification, Characterization, and Catalytic Application of Mesolite for One Pot Synthesis of 3-methyl-4-arylmethylene-isoxazol-5(4H)-ones. <em>Bulletin of Chemical Reaction Engineering &amp; Catalysis</em>, 12 (1): 32-40 (doi:10.9767/bcrec.12.1.655.32-40)<p><strong>Permalink/DOI:</strong> http://dx.doi.org/10.9767/bcrec.12.1.655.32-40</p><p> </p>