Kamal K. Pant

Catalytic and mechanistic insights into the production of ethyl levulinate from biorenewable feedstocks

The importance of ethyl levulinate (EL) as a fuel additive and a potential biomass-derived platform molecule is noteworthy. EL is obtained from the esterification of levulinic acid (LA) in the presence of ethanol. Besides LA, the acid-catalyzed ethanolysis reaction to produce EL can be carried out on a variety of biomass-derived substrates including furfuryl alcohol (FAL), chloromethyl furfural, monosaccharides, polysaccharides and lignocellulosic biomass. The acid catalysts employed for such conversions cover a wide range of structure and properties. The nature of the acid catalysts and the key intermediates formed during the reaction dictate the overall yield of the desired product. For example, in the ethanolysis reaction of FAL to produce EL, diethyl ether (DEE) and ethoxymethylfuran (EMF) produced as side products are suggested to influence the selectivity of EL. Similarly, in the ethanolysis of glucose, formation of ethyl-D-glucopyranoside (EDGP) results in a slow conversion to product EL. The review, therefore, focuses on highlighting the importance of catalyst structure, acidity and reaction mechanism and the role of key intermediates in the production of EL from biorenewable resources.

Perennial grass (Arundo donax L.) as a feedstock for thermo-chemical conversion to energy and materials

In the present study, perennial grass species Arundo donax L. was pyrolysed in a fixed-bed reactor and characterization was performed for the liquid and the solid products. The effect of process parameters such as temperature (350-650 °C), heating rate (10 °C and 40 °C min(-1)) and sweeping gas flow rate (50-250 ml min(-1)) was also investigated. Maximum bio-oil yield of ∼ 26% was observed at 500 °C for the heating rate of 40 °C min(-1). Chemical composition of the bio-oil was analysed through NMR, FTIR and GC-MS. The biochar was characterized by Scanning Electron Microscopy (SEM), Fourier Transform Infrared (FTIR) spectroscopy along with elemental analysis (CHN). The biochar produced as a co-product of A. donax pyrolysis can be a potential soil amendment with multiple benefits including increased soil fertility and C-sequestration. Current investigation suggests suitability of A. donax as a potential feedstock for exploitation of energy and biomaterials through pyrolytic route.

Pyrolysis of n-heptane: kinetics and modeling

Abstract The kinetics and product distribution during the pyrolysis of n -heptane have been investigated in the temperature range 953–1023 K at atmospheric pressure, with steam as the inert diluent. The overall n -heptane decomposition can be represented by a first-order reaction with a frequency factor of 6.02 × 10 13 s −1 and an activation energy of 250.7 kJ mol −1 . The experimental product yields could be satisfactorily modeled by use of a molecular reaction scheme, consisting of a first-order primary reaction and 24 secondary reactions among the primary products.

Direct conversion of natural gas to higher hydrocarbons： A review

Direct conversion of methane to higher hydrocarbons is an effective process to solve the problem of natural gas utilization. Although remarkable progress has been achieved on the dehydro-aromatization of methane (DAM), low conversion caused by severe thermodynamic limitations, coke formation, and catalysis deactivation remain important drawbacks to the direct conversion process. Molybdenum catalysts supported on HZSM-5 type zeolite support are among the most promising catalysts. This review focuses on the aspects of direct methane conversion, in terms of catalysts containing metal and support, reaction conditions, and conversion in different types of reactors. The reaction mechanism for this catalytic process is also discussed.

Extraction of nickel from spent catalyst using fresh and recovered EDTA

This study investigates the possibility of recovering nickel from spent catalyst (NiO/Al(2)O(3)) used in the fertilizer industry. EDTA (ethylenediaminetetraaceticacid) di sodium salt was used as a chelating to extract the Ni after which sulfuric acid was added to obtain NiSO(4). The dechelation process takes 5-6h to break the complex and EDTA which was recovered as H(4)EDTA acid in the solid form and solution contains NiSO(4). The objective was to evaluate the nickel removal efficiency of EDTA and reusability of recovered EDTA. The parameters affecting nickel recovery were EDTA concentration, time of chelation, catalyst to liquid ratio (s:l), mixing speed, pH and catalyst particle size. The extraction was up to 95% under the following conditions: 0.8M concentration of EDTA, solid to liquid ratio 1:50 (g/ml), particle size 100 microm, pH 10, 10h of chelation time, 700 rpm and 100 degrees C. Up to 95% of the EDTA could be recovered without losing significant activity.

Hydrogen production from steam reforming of acetic acid over Cu–Zn supported calcium aluminate

Hydrogen can be produced by catalytic steam reforming (CSR) of biomass-derived oil. Typically bio oil contains 12-14% acetic acid; therefore, this acid was chosen as model compound for reforming of biooil with the help of a Cu-Zn/Ca-Al catalyst for high yield of H(2) with low CH(4) and CO content. Calcium aluminate support was prepared by solid-solid reaction at 1350°C. X-ray diffraction indicates 12CaO·7Al(2)O(3) as major, CaA(l4)O(7) and Ca(5)A(l6)O(14) as minor phases. Cu and Zn were loaded onto the support by wet-impregnation at 10 and 1wt.%, respectively. The catalysts were characterized by Brunauer-Emmett-Teller (BET), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy TEM and the surface area for both support and Cu-Zn were 10.5 and 5.8m(2)/g, respectively. CSR was carried out in a tubular fixed bed reactor (I.D.=19mm) at temperatures between 600 and 800°C with 3-g loadings and (H(2)O/acetic acid) wt. ratio of 9:1. Significantly high (80%) yield of hydrogen was obtained over Cu-Zn/Ca-Al catalyst, as incorporation of Zn enhanced the H(2) yield by reducing deactivation of the catalyst. The coke formation on the support (Ca-12/Al-7) surface was negligible due to the presence of excess oxygen in the 12CaO·7Al(2)O(3) phase.

Intermediate pyrolysis of agro-industrial biomasses in bench-scale pyrolyser: Product yields and its characterization.

Pyrolysis of woody biomass, agro-residues and seed was carried out at 500 ± 10 °C in a fixed bed pyrolyser. Bio-oil yield was found varying from 20.5% to 47.5%, whereas the biochar and pyrolysis gas ranged from 27.5% to 40% and 24.5% to 40.5%, respectively. Pyrolysis gas was measured for flame temperature along with CO, CO2, H2, CH4 and other gases composition. HHV of biochar (29.4 MJ/kg) and pyrolitic gas (8.6 MJ/kg) of woody biomass was higher analogous to sub-bituminous coal and steam gasification based producer gas respectively, whereas HHV of bio-oil obtained from seed (25.6 MJ/kg) was significantly more than husks, shells and straws. TGA-DTG studies showed the husks as potential source for the pyrolysis. Bio-oils as a major by-product of intermediate pyrolysis have several applications like substitute of furnace oil, extraction of fine chemicals, whereas biochar as a soil amendment for enhancing soil fertility and gases for thermal application.

Pyrolysis of methylcyclohexane: Kinetics and modelling

Abstract Steam pyrolysis of methylcyclohexane has been investigated in a tubular reactor at atmospheric pressure in the temperature range 953-1073 K. Using non-linear regression, the overall decomposition was found to be approximately first-order with a pre-exponential factor and activation energy of 1.7110 11 s −1 and 209.0 kJ mol −1 , respectively. The experimental product yields and conversion could be satisfactorily simulated using a molecular model consisting of an overall primary reaction and twenty-four secondary reactions.

Greener approach for the extraction of copper metal from electronic waste.

Technology innovations resulted into a major move from agricultural to industrial economy in last few decades. Consequently, generation of waste electronic and electrical equipments (WEEE) has been increased at a significant rate. WEEE contain large amount of precious and heavy metals and therefore, can be considered a potential secondary resource to overcome the scarcity of metals. Also, presence of these metals may affect the ecosystem due to lack of adequate management of WEEE. Building upon our previous experimental investigations for metal extraction from spent catalyst, present study explores the concept of green technology for WEEE management. Efforts have been made to recover base metal from a printed circuit board using eco-friendly chelation technology and results were compared with the conventional acid leaching method. 83.8% recovery of copper metal was achieved using chelation technology whereas only 27% could be recovered using acid leaching method in absence of any oxidant at optimum reaction conditions. Various characterization studies (energy dispersive X-ray analysis, scanning electron microscopy, X-ray diffraction, inductive coupled plasma spectrophotometry) of Printed Circuit Board (PCB) and residues were performed for qualitative and quantitative analysis of samples. Significant metal extraction, more than 96% recovery of chelating agent, recycling of reactant in next chelation cycle and nearly zero discharge to the environment are the major advantages of the proposed green process which articulate the transcendency of chelation technology over other conventional approaches. Kinetic investigation suggests diffusion controlled process as the rate determining step for the chelate assisted recovery of copper from WEEE with activation energy of 22kJ/mol.

Potassium-containing calcium aluminate catalysts for pyrolysis of n-heptane

Abstract The effectiveness of potassium promoted calcium aluminate to catalyze the steam pyrolysis of n-heptane has been investigated at 1023 K and atmospheric pressure. Various amounts of potassium were incorporated on calcium aluminate (12CaO7Al2O3) by three different methods. Compared to thermal pyrolysis, addition of the calcium aluminate catalyst (either promoted or unpromoted) significantly increased the conversion as well as the yields of CH4, C2H4 and C3H6. The presence of potassium significantly reduced the coke deposited on the catalysts due to the enhanced rate of the coke gasification reaction. A significant amount of potassium was lost from the catalysts during preparation as well as during reaction. The gasification activity was higher for the catalysts in which the K2CO3 was incorporated by incipient wetness method but the potassium loss during reaction was also higher in comparison to catalysts in which the potassium was incorporated by co-sintering.