Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

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CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

 

 

Special Issue on Carbon Dioxide Capture, Sequestration & Utilization

 

VOLUME 51A

NUMBER 9-10

SEPT-OCT 2012

CONTENTS

Carbon dioxide capture and sequestration

 

1201

 

Techno-economic aspects of the post-combustion CO2 capture processes

 

 

 

 

 

 

 

 

 

 

 

 

 

P S Sai Prasad* & K V Raghavan

 

 

 

The techno-economic aspects of post-combustion carbon capture technologies are reviewed. Projections for the future are suggested.

 

 

GA_

 

 

 

1214

 

Carbon dioxide capture using amine functionalized
silica gel

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Tushar Sakpal, Asheesh Kumar, Sanjay Kamble & Rajnish Kumar*

 

 

 

Silica gel loaded with amine functionality using poly(ethyleneimine) and (3-aminopropyl)-trimethoxysilane shows significant CO2 uptake as compared to bare silica gel. Irrespective of CO2 capture efficiency, the comparatively simpler process of attaching amine functionality in the former makes it an ideal candidate for large scale application like separation of CO2 from  flue gas mixture.

 

IC3507-GA

 

 

1223

 

Carbon dioxide capture by metal organic frameworks

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Subhadeep Saha, Suman Chandra, Bikash Garai & Rahul Banerjee*

 

 

 

MOFs require less energy for CO2 adsorption and regeneration than materials relying on chemisorptions. To achieve high adsorption capacity, fast CO2 adsorption-desorption and low energy requirement for regeneration are necessary. In this review several possibilities for increasing the CO2 adsorption capacity of MOFs, for instance, introduction of open metal sites and the use of ligand molecules with specific functionalities (like -OH or -NH2) have been described.

 

GA

 

 

1231

 

Selective CO2 uptake in a bi-pillared layer 3D metal organic framework of Zn(II)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ritesh Haldar, Raghu Pradeep Narayan &
Tapas Kumar Maji
*

 

 

 

A bi-pillared layer 3D microporous metal organic framework has been synthesized and is shown to exhibit selective adsorption of CO2 gas over other gases like N2, Ar and H2 at
195 K. This has been correlated to the highly polar pore surfaces.

 

 

GA_Final

 

1238

 

 

Adsorption  selectivity of CO2 over N2 by cation exchanged zeolite L: Experimental and simulation studies

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ganga P Dangi, Munusamy K, Rajesh S Somani* & Hari C Bajaj*

 

 

 

CO2 and N2 adsorptions of alkali and alkaline earth metal cation exchanged zeolite L have been studied at 293 and 303 K. The observed CO2 capacity is highest for LiL where the ion-quadrupole interaction is dominant. However, the highest CO2/N2 selectivity is obtained for CaL, which provides high separation and better capacity for CO2.

 

 

IC3503-GA

 

Carbon dioxide utilization

 

1252

 

 

Carbon dioxide – A potential raw material for
the production of fuel, fuel additives and
bio-derived chemicals

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sivashunmugam Sankaranarayanan &
Kannan Srinivasan
*

 

 

 

Carbon dioxide can effectively be utilized for the production of fuels and fuel additives. CO2 can also play a vital role in the value addition of biomass by producing organic carbonates via further biorefining processes. Utilizing CO2 in large quantities through these routes can make a positive impact on the environment.

 

IC 3516 Graphical Abstract_SC

 

 

 

1263

 

 

Titania based catalysts for photoreduction of carbon dioxide: Role of modifiers

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

V Jeyalakshmi, R Mahalakshmy, K R Krishnamurthy & B Viswanathan*

 

 

 

Implications of modifications on the
electronic structure of TiO2

 

 

IC 3502_GA.tif

 

 

 

1284

 

Analysis of pyridinium catalyzed electrochemical and photoelectrochemical reduction of CO2: Chemistry and economic impact

 

 

 

 

 

 

 

 

 

 

 

 

Kate Keets, Emily Barton Cole, Amanda J Morris, Narayanappa Sivasankar, Kyle Teamey,  
Prasad S Lakkaraju * & Andrew B Bocarsly
*

 

 

 

A review of recent research on the electrochemical and photoelectrochemical reduction of carbon dioxide mediated by pyridinium radical is presented. A preliminary account of the economic analysis shows that combined electrochemical and thermal conversion process is the most cost effective.

 

 

 

1298

 

Reactions in supercritical carbon dioxide

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Mayadevi

 

 

 

Recent developments in hydrogenation, hydroformylation, oxidation, C-C coupling, alkylation, acetylation and esterification reactions in supercritical carbon dioxide are reviewed.

 

 

1306

 

 

Metal organic frameworks as catalysts in the conversion of CO2 to cyclic carbonates

 

 

 

 

 

 

 

 

 

 

 

 

 

Moises A Carreon

 

 

 

The catalytic activity of two prototypical metal organic frameworks, namely, ZIF-8 and Cu3(BTC)2, in the synthesis of chloropropene carbonate from CO2 and epichlorohydrin is presented.

 

 

IC3504-GA

 

 

1315

 

Utilization of carbon dioxide in oxidative dehydrogenation reactions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

G Raju, Benjaram M Reddy* & Sang-Eon Park

 

 

 

CO2 is utilized as a soft oxidant in oxidative dehydrogenation of ethylbenzene and n-butane to the respective olefins over zirconia-based mixed oxide catalysts. Among various combinations, CeO2−V2O5/TiO2−ZrO2 and VOx/SnO2−ZrO2 catalysts exhibit high activity and selectivity.

 

IC 3501_GA_White.tif   

 

1325

 

CuII-exchanged montmorillonite K10 clay-catalyzed direct carboxylation of terminal alkynes with
carbon dioxide

 

 

 

 

 

 

 

 

 

 

 

Ravindra D Aher, Madhuri H Gade, R Santhosh Reddy & Arumugam Sudalai*

 

 

 

 

CS 08_GA

 

1330

 

Synthesis of 1,2-glycerol carbonate from carbon dioxide: The role of methanol in fluid phase equilibrium

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Podila, L Plasseraud, H Cattey, D Ballivet-Tkatchenko*, G V S M Carrera, M Nunes da Ponte, S Neuberg & A Behr

 

 

 

In the synthesis of 1,2-glycerol carbonate from CO2, the
reaction takes place in the liquid phase where methanol dissolves glycerol, CO2, and the tin complex. Increasing CO2 pressure separates methanol from glycerol, thus inhibiting the formation of
1,2-glycerol carbonate.

 

 

Graphical abstract

 

 

1339

 

Carbon dioxide reforming of methane over ruthenium substituted strontium titanate perovskite catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hanmant R Gurav, Richa Bobade,
Vineetha Lakshmi Das & Satyanarayana Chilukuri
*

 

 

 

Ruthenium doped SrTiO3 perovskite catalysts show good catalytic performance in dry reforming of methane to give 95.5 % CO2 and 93 % CH4 conversions at a high GHSV of 28,800 h-1. Very little deactivation of the catalysts is observed even after 100 h after reaction. Reverse water gas shift reaction is dominant on these catalysts, particularly in the low temperature region (873–973 K).

 

 

Fig 8-GHSV Corr

 

 

 

1348

 

Pt nanoparticles supported on mesoporous ZSM-5:
A potential catalyst for reforming of methane with carbon dioxide

 

 

 

 

 

 

 

 

 

 

 

 

Bipul Sarkar, Shashank Suman, Ritesh Tiwari,
Rajib Kumar Singha, Shilpi Ghosh, Shankha,
Shubhra Acharyya,  L N Sivakumar Konathala, Chandrashekar Pendem, Kshudiram Mantri & Rajaram Bal
*

 

 

 

Pt-nanoparticles supported on ZSM-5 show 70.3 % methane conversion and almost 100 % selectivity with H2/CO ratio of
≥ 0.97. On increasing the Pt loading (> 2%), agglomeration of
Pt occurs and the activity decreases. However, the catalyst
is stable and the deactivation is negligible even after 24 h of
time-on-stream study.

 

 

IC3506-GA

 

 

1354

 

Chitosan biohydrogel beads: A recyclable, biodegradable, heterogeneous catalyst for the regioselective synthesis of 5-aryl-2-oxazolidinones from carbon dioxide and aziridines at mild conditions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rahul A Watile & Bhalchandra M Bhanage*

 

 

 

Chitosan biohydrogel beads serve as an efficient, inexpensive, heterogeneous and recyclable catalyst for coupling of CO2 with various aziridines under mild reaction conditions. The proposed process represents a simple, green and cost-effective route to synthesize 5-aryl-2-oxazolidinones with good yields and excellent regioselectivity, along with easy catalyst recycling.

 

IC3510-GA

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1201-1213

 

 

Techno-economic aspects of the post-combustion CO2 capture processes

P S Sai Prasad* & K V Raghavan

CSIR-Indian Institute of Chemical Technology, Uppal Road, Hyderabad 500 007, India

Email: saiprasad@iict.res.in (PSSP)/ kondapuramiict@yahoo.com (KVR)

Received 4 July 2012; revised and accepted 27 July 2012

With the growing awareness on global warming, carbon capture and sequestration has gained enormous importance. This report focuses attention on the various materials and methodologies available for CO2 capture, particularly from stationary sources like thermal power plant emissions. The current state of development and future prospects are highlighted. The economic impact of capture technologies on the cost of power production is discussed and the way forward for their large-scale application is proposed. The primary aim of this review is to identify vital development pathways that need to be pursued to accelerate the large scale deployment of post combustion CO2 capture technologies.

Keywords: Carbon dioxide capture, Post-combustion carbon dioxide capture processes, Gas-liquid absorptions, Gas-solid adsorptions, Membrane separations

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1214-1222

 

 

Carbon dioxide capture using amine functionalized silica gel

Tushar Sakpal, Asheesh Kumar, Sanjay Kamble & Rajnish Kumar*

Chemical Engineering and Process Development Division,
CSIR-National Chemical Laboratory, Pune 411 008, India

Email: k.rajnish@ncl.res.in

Received 1 June 2012; revised and accepted 18 June 2012

Commercially available silica gel is chemically modified for carbon dioxide capture. Calcinated silica gel of certain particle size functionalized with amine using two different methods, wet impregnation and grafting via silane chemistry has been employed as a porous media. The prepared material is characterized by Fourier transform infrared, scanning electron microscopy, energy dispersive analysis of X-rays, thermogravimetry and N2 physisorption techniques. Gas uptake measurements have been carried out to ascertain the CO2 capture capacity of the amine functionalized material. The experiments have been carried out at moderate pressure and temperature range to ascertain its potential for easy scale up.

Keywords: Carbon dioxide capture, Amine functionalized silica gel, Poly(ethyleneimine), Wet impregnation, Grafting, Silane chemistry

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1223-1230

 

 

Carbon dioxide capture by metal organic frameworks

Subhadeep Saha, Suman Chandra, Bikash Garai & Rahul Banerjee*

Physical and Materials Chemistry Division, CSIR-National Chemical Laboratory,
Dr Homi Bhabha Road, Pune 411 008, India

Email: r.banerjee@ncl.res.in
Received 23 June 2012; revised and accepted 21 August 2012

 

The design and synthesis of functionalized metal organic framework  materials (MOFs) for reversible physisorption of CO2 is discussed. This strategy of CO2 adsorption in MOFs requires less energy for regeneration than materials relying on chemisorption. As a result the MOFs have received considerable attention as sorbent materials for strategic gases such as CO2 and H2. In this review, we have discussed different MOFs and hybrid materials containing MOFs which can adsorb CO2 at room temperature. In order to achieve high adsorption capacity, fast CO2 adsorption-desorption and low energy requirement for regeneration are necessary. Several avenues for increasing the CO2 adsorption capacity of such materials, for instance, introduction of open metal sites and the use of ligand molecules with specific functionalities (like -OH or -NH2) have been described. It has been observed that CO2 loading capacity of MOFs increases with functionalization. Herein, we have discussed how N-containing and fluorinated MOFs are designed to achieve higher CO2 loading than their non-functionalized counterparts. Nanocarbons (e.g. carbon nanotubes, carbon nanofibres, etc.) are porous materials and a blend of these porous materials with porous MOFs or porous carbon derived from MOFs may act as a better adsorbate than even the pure materials. Enhancement of CO2 loading by nanocarbon-MOF hybrid material is also discussed.

Keywords: Metal organic frameworks, Carbon dioxide capture, Carbon dioxide adsorbents, Porous nanocarbons, Nanocarbons, Hybrid materials

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1231-1237

 

 

Selective CO2 uptake in a bi-pillared layer 3D metal-organic
framework of Zn(II)

Ritesh Haldara, Raghu Pradeep Narayanb & Tapas Kumar Majia, b, *

Molecular Materials Laboratory, aNew Chemistry Unit and bChemistry and Physics of Materials Unit
Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore 560 064, India

Email: tmaji@jncasr.ac.in

Received 12 July 2012; revised & accepted 18 August 2012

A new two-fold interpenetrated 3D bi-pillared framework, {[Zn(1,4-bdc)(azbpy)]∙DMF}n (1), where 1,4-bdc = 1,4-benzene dicarboxylic acid, azbpy = 4,4′- azobipyridine and DMF = N,N-dimethyl formamide, has been synthesized from a mixed ligand system and characterized by single crystal as well as powder X-ray diffraction and thermogravimetric analysis. The metal center, Zn(II), having a trigonal bi-pyramidal geometry, is connected to the three different 1,4-bdc linkers in the equatorial positions while the axial positions are occupied by the two different 4,4′-azbpy pillars. The framework contains one-dimensional rectangular shaped channels along the c axis and the channel surfaces are decorated with the nitrogen atoms of –N=N- functional group from azbpy ligand. The desolvated framework has a specific surface area of ~ 40 m2 g-1 and shows excellent selective uptake of CO2 at 195 K among other small gases like Ar, N2 and H2. (1) also adsorbs acetonitrile and benzene solvent vapors at 298 K.

Keywords: Metal organic frameworks, Selective CO2 adsorption, Polar pore surface, Solvent vapour adsorption

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1238-1251

 

 

Adsorption selectivity of CO2 over N2 by cation exchanged zeolite L:
Experimental and simulation studies

Ganga P Dangi, Munusamy K, Rajesh S Somani* & Hari C Bajaj*

Discipline of Inorganic Materials and Catalysis,
CSIR-Central Salt & Marine Chemicals Research Institute,
GB Marg, Bhavnagar 364 021, Gujarat, India

Email: rssomani@csmcri.org (RSS)/ hcbajaj@csmcri.org (HCB)

Received 25 May 2012; revised and accepted 18 June 2012

CO2 and N2 adsorptions of alkali and alkaline earth metal cation exchanged zeolite L have been investigated by volumetric measurements and Grand Canonical Monte Carlo simulation. The zeolite KL shows lower degree of exchange because of its unique open-channel framework, linked cancrinite and intercage sites. Structural characteristics have been evaluated using X-ray diffraction analysis and surface area measurements. CO2 and N2 adsorption isotherms have been obtained for zeolite KL and its cation exchanged form up to 101.3 kPa at 293 and 303 K and the corresponding heats of adsorption estimated by the Clausius-Clapeyron equation. The experimental results are compared with those obtained from GCMC simulation. The texture of the materials and their selectivity for CO2 over N2 adsorption varies with the nature of the exchanged cations. Zeolite-CaL shows remarkably high CO2 selectivity (31 times) over N2 amongst the studied alkali and alkaline cation exchanged zeolite L. It has been shown that zeolite L can be used as a potential adsorbent for the removal of CO2 from industrial effluent gases.

Keywords: Zeolites, Alkali metals, Alkaline earth metals, Ion exchange, Gas adsorption, Carbon dioxide adsorption,Nitrogen adsorption, Grand Canonical Monte Carlo simulation

 

 

Carbon dioxide utilisation

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1252-1262

 

 

Carbon dioxide – A potential raw material for the production of fuel,
fuel additives and bio-derived chemicals

Sivashunmugam Sankaranarayanan & Kannan Srinivasan*

Discipline of Inorganic Materials and Catalysis, CSIR-Central Salt and Marine Chemicals Research Institute,
Gijibhai Bhadheka Marg, Bhavnagar 364 002,
India

Email: skannan@csmcri.org/ kanhem1@yahoo.com

Received 12 July 2012; revised and accepted 18 August 2012

Amongst the various greenhouse gases emitted into the atmosphere, carbon dioxide emission is the highest in terms of tonnage and has been identified as a predominant source contributing to climate change. Owing to its abundance through anthropogenic sources, it is highly desirable to utilize CO2 to produce valuable products, in particular fuels and large volume chemicals, and thereby mitigate significantly its environmental impact. This review aims to cover the attempts made in utilizing CO2 for the production of fuels, fuel additives and bio-derived chemicals, in particular organic carbonates. Although this review does not intend to encompass the literature in the holistic manner, it does endeavor to provide recent approaches, difficulties, challenges and offer perspective in the years to come on this important area of research.

Keywords: Carbon dioxide utilization, Raw material for fuel production, Syngas, Methane, Dimethyl carbonate, Fatty cyclic carbonate, Glycerol carbonate

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1263-1283

 

 

Titania based catalysts for photoreduction of carbon dioxide: Role of modifiers

V Jeyalakshmia, b, R Mahalakshmya, K R Krishnamurthyb & B Viswanathanb, *

aDepartment of Chemistry, Thiagarajar College, Madurai Kamaraj University, Madurai 625 021, Tamil Nadu, India

bNational Centre for Catalysis Research, Indian Institute of Technology Madras, Chennai 600 036, Tamil Nadu, India

Email: bvnathan@iitm.ac.in

Received 24 May 2012; revised and accepted 22 June 2012

Photocatalytic conversions on titania utilizing sunlight as the energy source have been studied extensively for a variety of processes/ synthesis, like removal of pollutants in air and liquid streams, self-cleaning, anti-fogging and anti-bacterial applications, splitting of water into hydrogen and oxygen and photoreduction of CO2 by water to yield hydrocarbons. These processes are receiving global attention as an off-shoot of the frantic search for alternative energy sources. Though titania continues to be the preferred catalyst in view of its low toxicity, ability to resist photo-corrosion, versatility, and abundant availability at low cost, critical limitations do exist in terms of its inability to get activated with visible light and in achieving high conversion efficiency and quantum yield. Several techniques of modifying titania to improve its performance have evolved over the years resulting in correlations and concepts on structure-property-activity and the role of preparation methods. Such modifications have lead to changes in light absorption efficiency, electronic structure, energy levels, morphology, phase composition and other photophysical properties with moderate improvements in the performance. Efforts to understand the mode of action of the modifiers in terms of the first principles, i.e., rationalization of the activity in terms of electronic and structural properties and establishing theoretical basis for the photocatalytic action, have met with only partial success, due to conflicting observations/results.

The objectives towards modifications, namely, extending the light absorption range, retarding charge carrier
re-combination, facilitating their fast transport to the active sites on titania surface and incorporation of active elements suitable for redox reactions, have been achieved to a reasonable level. However, commensurate improvement in activity/CO2 conversion has not been observed. Maximization of selectivity (to methane or methanol) and arresting catalyst deactivation are the two major issues yet to be understood in clear terms. An in-depth study to understand the surface transformations at molecular level under activation by light energy, is needed to achieve further improvements in the activity of the catalysts and the process. This review brings forth an account of the investigations on modified titania, capturing some significant and selected contributions out of the vast literature available, with an emphasis on application for photocatalytic reduction of CO2 with water.

Keywords: Photocatalysts, Photoreduction, Carbon dioxide photoreduction, Photophysical properties, Titania, Solar energy

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1284-1297

 

 

Analysis of pyridinium catalyzed electrochemical and photoelectrochemical reduction of CO2: Chemistry and economic impact

Kate A Keets a, Emily Barton Colea, Amanda J Morrisc, Narayanappa Sivasankara, Kyle Teameya,
Prasad S Lakkarajub, c, * & Andrew B Bocarslyc, *

aLiquid Light Inc, Monmouth Junction, New Jersey, USA

bDepartment of Chemistry, Georgian Court University, New Jersey, USA

cDepartment of Chemistry, Princeton University, Princeton, New Jersey, USA

Email: bocarsly@princeton.edu (ABB)/ prasadl@princeton.edu (PSL)

Received 9 June 2012; revised and accepted 22 June 2012

This review highlights the recent work related to the electrochemical and photoelectrochemical conversion of carbon dioxide into methanol and formic acid. Information related to the structural, mechanistic and kinetic aspects of the pyridinium and imidazolium catalyzed reduction processes is presented. The economic impact of these processes is delineated by calculating the cost per billion gallons of gasoline equivalence for methanol by three methods viz., electrochemical conversion, photoelectrochemical conversion, combined electrochemical conversion and thermal conversion. Our initial analysis shows that the last method may be the most economically feasible method under the existing technologies.

Keywords: Electrochemical reduction, Photoelectrochemical reduction, Carbon dioxide reduction, Pyridinium catalysed reactions, Imidazolium catalysed reactions

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1298-1305

 

 

Reactions in supercritical carbon dioxide

S Mayadevi

CEPD Division, CSIR-National Chemical Laboratory, Pune 411 008, India

Email: s.mayadevi@ncl.res.in

Received 20 June 2012; revised and accepted 12 July 2012

Use of conventional organic solvents often leads to the formation of hazardous waste, the disposal of which is a matter of environmental concern. Carbon dioxide is considered to be a green reaction medium and a good replacement for conventional organic solvents as it is benign and leads to elimination/reduction of hazardous wastes. Use of CO2 at near/above critical conditions has several additional advantages as the reactions can be pressure-tuned to eliminate transport resistance, increase solvent power and heat capacity. Hence, there has been considerable interest in the use of supercritical carbon dioxide as either a replacement of conventional organic solvent or as a co-solvent in reactions. Herein, recent developmenst in this area during the last decade is reviewed, specifically in gas-liquid (organic hydrogenation, hydroformylation and oxidation) and liquid-liquid (carbon-carbon coupling, alkylation, acetylation, esterification) reactions.

Keywords: Hydrogenation, Hydroformylation, Oxidation, Alkylation, Supercritical carbon dioxide, Carbon dioxide

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1306-1314

 

 

Metal organic frameworks as catalysts in the conversion of
CO2 to cyclic carbonates

Moises A Carreon

Department of Chemical Engineering, University of Louisville, Louisville, KY, 40292, USA
Email: macarr15@louisville.edu

Received 29 May 2012; revised and accepted 14 June 2012

The effective utilization of CO2 as a renewable raw material for the production of useful chemicals is an area of enormous interest. In particular, the catalytic conversion of CO2 into cyclic carbonates, which are useful chemical intermediates employed for the production of plastics and organic solvents, represents an attractive route for the efficient use of carbon dioxide. The development of superior performance catalysts requires novel materials with fundamentally different structural, compositional, adsorption and transport properties than those of conventional zeolite, metal oxides or metal phases. In this respect, metal organic frameworks have emerged as a novel type of crystalline porous materials which combine highly desirable properties, such as uniform micropores, high surface areas, flexible chemistries and exceptionally high thermal and chemical stability, making them ideal candidates for catalytic applications. Herein, we discuss the catalytic activity of two prototypical metal organic frameworks, namely ZIF-8 and Cu3(BTC)2 in the synthesis of chloropropene carbonate from CO2 and epichlorohydrin.

Keywords: Metal organic frameworks, Heterogenous catalysts, Cycloaddition reactions, Cyclic carbonates,
Carbon dioxide conversion

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1315-1324

 

 

Utilization of carbon dioxide in oxidative dehydrogenation reactions

G Rajua, Benjaram M Reddya, * & Sang-Eon Parkb

aInorganic and Physical Chemistry Division, CSIR – Indian Institute of Chemical Technology,
Uppal Road, Tarnaka, Hyderabad 500 607, India
Email: bmreddy@iict.res.in/ mreddyb@yahoo.com

bLaboratory of Nano-Green Catalysis, Department of Chemistry, Inha University,
253 Yonghyun-dong, Incheon 402-751, Republic of Korea
Email: separk@inha.ac.kr

Received 16 May 2012; revised and accepted 18 June 2012

Utilization of CO2 as a feedstock for synthesis of chemicals is an alternate and most promising option for CO2 abatement. In the present study, CO2 has been utilized as a soft oxidant for oxidative dehydrogenation of ethylbenzene and n-butane to the corresponding olefins. For this, TiO2−ZrO2 (TZ) mixed oxide-supported V2O5, CeO2 and V2O5–CeO2 catalysts has been synthesized, characterized and evaluated for the oxidative dehydrogenation reactions. The physicochemical characterization has been achieved by various techniques such as, powder X-ray diffraction, CO2 and NH3 temperature-preprogrammed desorption, temperature-preprogrammed reduction, X-ray photoelectron spectroscopy and BET surface area methods. XRD analysis of the samples calcined at 550 °C indicates that the impregnated active components are in a highly dispersed state on the support. XP spectra shows the existence of vanadium and cerium in V4+ and Ce4+/Ce3+ oxidation states, respectively. Among the various catalysts investigated, V2O5−CeO2/TiO2−ZrO2 exhibits a high conversion and product selectivity for the oxidative dehydrogenation of ethyl benzene. On the other hand, a high conversion and selectivity in the oxidative dehydrogenation of n-butane is noted over V2O5/SnO2−ZrO2 mixed oxide catalyst. The combined acid–base and redox properties of the catalysts play a major role in these reactions. In particular, the characterization studies reveal that mixed oxides show a high specific surface area, superior acid-base properties and better redox characteristics. All these properties enhance the catalytic performance of mixed oxide catalysts.

Keywords: Ethylbenzene, n-Butane, Styrene, C4 olefins, Oxidative dehydrogenation, Carbon dioxide abatement, Dehydrogenation, Mixed oxide catalysts, Supported catalysts, Titania, Zirconia, Ceria, Vanadia

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1325-1329

 

 

CuII-exchanged montmorillonite K10 clay-catalyzed direct carboxylation of terminal alkynes with carbon dioxide

 

Ravindra D Aher, Madhuri H Gade, R Santhosh Reddy & Arumugam Sudalai*

Chemical Engineering and Process Development Division, CSIR-National Chemical Laboratory,
Pashan Road, Pune 411 008, India
Email: a.sudalai@ncl.res.in

Received 8 June 2012; revised and accepted 29 June 2012

A new, simple and straight-forward protocol for direct carboxylation of terminal alkynes has been developed using CuII-montmorillonite K10 clay as a heterogeneous catalyst and CO2 as the C1 carbon feedstock. Also coupling of terminal alkynes with CO2 (1 atm) in the presence of alkyl halides has been achieved under the same reaction conditions, thereby providing access to a variety of functionalized alkyl-2-alkynoates in high yields.

Keywords: Catalysts, Montmorillonite clays, Carboxylation, Carbon dioxide activation, Alkyne C-H activation, Alkyl esters

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1330-1338

 

 

Synthesis of 1,2-glycerol carbonate from carbon dioxide: The role of methanol in fluid phase equilibrium

S Podila, L Plasseraud, H Cattey & D Ballivet-Tkatchenko*

Université de Bourgogne, CNRS, UMR 6302, Institut de Chimie Moléculaire, 9, Avenue Alain Savary
21000 Dijon, France

Email: ballivet@u-bourgogne.fr

and

G V S M Carrera & M Nunes da Ponte

REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa
2829-516 Caparica, Portugal

Email: mnponte@fct.unl.pt

and

S Neuberg & A Behr

Department of Biochemical and Chemical Engineering, Technische Universität Dortmund, Emil-Figge Str. 66
44227 Dortmund, Germany

Email: Arno.Behr@bci.tu-dortmund.de

Received 2 July 2012; revised and accepted 26 July 2012

The effect of methanol on the synthesis of 1,2-glycerol carbonate from CO2 and glycerol is studied in the presence of Bu2Sn(OCH3)2, n-Bu2SnO, and tert-Bu2SnO. At 423 K, up to 2.7 mol% yield in glycerol carbonate, based on glycerol, could be obtained in the pressure range 14-20 MPa. Addition of acetonitrile promotes notably the yield to 7 mol%. Fluid phase equilibrium experiments with the ternary mixture CO2/glycerol/methanol show that the reaction takes place in a liquid phase where methanol dissolves glycerol, CO2, and the tin complexes. Above ~0.6 mole fraction, CO2 behaves as an anti-solvent, separating methanol from glycerol, thus inhibiting the formation of 1,2-glycerol carbonate. Dimethyl carbonate is a side-product of glycerol carbonation resulting mainly from transesterification between glycerol carbonate and methanol. Glycerol coordination to tin center is evidenced by the isolation of di-tert-Bu2Sn(1,2-glycerolate) complex. Its structure determination by single-crystal X-ray diffraction shows that the remaining OH group of glycerol promotes the formation of one-dimensional polymeric chain.

Keywords: Glycerol, Glycerol carbonate, Carbon dioxide, Methanol, Fluid phase equilibrium, Vapour-liquid equilibrium, Dibutyltin glycerolate, X-ray structure

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1339-1347

 

 

Carbon dioxide reforming of methane over ruthenium substituted strontium titanate perovskite catalysts

Hanmant R Gurav, Richa Bobade, Vineetha Lakshmi Das & Satyanarayana Chilukuri*

Catalysis Division, CSIR-National Chemical Laboratory, Dr. Homi Bhaba Road, Pune 411 008, India

Email: sv.chilukuri@ncl.res.in

 

Received 8 August 2012; revised and accepted 20 August 2012

 

Strontium titanate (SrTiO3) doped with varying amounts of ruthenium (7.9, 15.6 and 31 wt%) have been prepared by the citrate gel synthesis method. Structural and textural characterizations reveal that at lower concentrations, a major part of Ru is incorporated in the lattice of SiTiO3. The content of surface Ru (outside lattice) increases with increasing amounts of the doped Ru. The surface Ru reduced at lower temperatures compared to Ru incorporated into the lattice. The reduction of the lattice substituted Ru occurs only at temperatures above the collapse of the perovskite structure. The catalyst sample with 7.9 wt% of Ru shows good conversions in the dry reforming of methane with CO2. The conversion of CO2 is in excess compared to methane under the studied reaction conditions. As a result, H2/CO ratio of the product gases which should have been equivalent to unity is lower than the stoichiometric value. This ratio is particularly low when lower reaction temperatures (873–973 K) were used. Similar was the case when high space velocities were used. Low methane conversion and reverse water gas shift reaction are the causes for the low H2/CO ratios.

Keywords: Carbon dioxide reforming, Dry reforming, Methane reforming, Catalysts, Doped catalysts, Ruthenium doped catalysts, Citrate gel method, Syngas, Reverse water gas shift, Perovskites, Strontium titanate

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1348-1353

 

 

Pt nanoparticles supported on mesoporous ZSM-5: A potential catalyst for reforming of methane with carbon dioxide

Bipul Sarkar, Shashank Suman, Ritesh Tiwari, Rajib Kumar Singha, Shilpi Ghosh, Shankha, Shubhra Acharyya,
L N Sivakumar Konathala, Chandrashekar Pendem, Kshudiram Mantri & Rajaram Bal*

Catalytic Conversion & Processes Division, CSIR-Indian Institute of Petroleum, Dehradun 248 005, India

Email: raja@iip.res.in

Received 31 May 2012; revised and accepted 22 June 2012

Pt-nanoparticles supported on ZSM-5 have been prepared and characterized by X-ray diffraction, field emission-scanning electron microscopy, X-ray photoelectron spectroscopy and N2 adsorption/desorption study. The catalyst shows very high methane conversion in the reforming of methane with CO2. The effect of Pt loading and various reaction parameters like temperature, gas hourly space velocity and time-on-stream have been examined during the course of study. It is found that the catalyst is stable and the deactivation negligible even after 24 h of time-on-stream study.

Keywords: Catalysts, Supported catalysts, Mesoporous catalysts, Colloidal nanoparticles, Platinum, Carbon dioxide, Methane reforming, Dry reforming, Syngas

 

 

Indian Journal of Chemistry

Vol. 51A, Sept-Oct 2012, pp. 1354-1360

 

 

Chitosan biohydrogel beads: A recyclable, biodegradable, heterogeneous catalyst for the regioselective synthesis of 5-aryl-2-oxazolidinones from
carbon dioxide and aziridines at mild conditions

Rahul A Watile & Bhalchandra M Bhanage*

Department of Chemistry, Institute of Chemical Technology, Matunga, Mumbai 400 019, India

Email: bm.bhanage@gmail.com/ bm.bhanage@ictmumbai.edu.in

Received 13 June 2012; revised and accepted 25 June 2012

In the search for efficient catalysts for a reaction under mild conditions, cycloaddition reactions of carbon dioxide with various aziridines catalyzed by chitosan biohydrogel beads without additional solvent and metal co-catalyst to form five-membered 5-aryl-2-oxazolidinones in high yields and selectivity has been studied. Reaction rate, conversion and selectivity are studied as a function of a series of input variables including catalyst loading, temperature, pressure and solvent system. The catalyst is easily recovered and has been reused in five consecutive cycles without any significant loss of its catalytic activity and selectivity. The catalyst, chitosan biohydrogel beads, has been characterized by a variety of techniques, namely, scanning electron microscopy and Fourier transform infrared spectroscopy. A plausible reaction mechanism for the hydrogen-bond assisted ring-opening of aziridine to five-membered 5-aryl-2-oxazolidinones is also proposed.

Keywords: Catalysts, Heterogeneous catalysts, Aziridines, 5-Aryl-2-oxazolidinones, Carbon dioxide, Chitosan biohydrogel beads