Ganapati V. Shanbhag

Heterogeneous catalysis

AlwinMittasch, a German chemist and scientific historian remarked in the early 20th century that “chemistry without catalysis would be like a sword without hilt, like a bell without ringing....” Nowadays, catalysts play a vital role in providing society fuels, commodity and fine chemicals, pharmaceuticals, polymers and means for protecting the environment. Around 90 % of all industrial chemical processes are catalytic. Among the catalysts, heterogeneous catalysts have advantages over homogenous counterparts such as easy catalyst separation, recyclability, no product contamination and environmentally benign. Though catalysis is the area of applied chemistry and has a lot of commercial importance, basic research in this area has also gained a lot of prominence. In the last decade (2001-2010), four Nobel prizes have gone to inventions on catalysts which itself shows the academic importance of the subject.However, direct inspiration for doing research in Catalysis can be drawn by its importance in solving the problems of social relevance like desire for green and renewable fuels, reducing environmental pollution by making clean chemical processes andimproving the product yield by designing better catalysts leads to cheaper products.Designing an efficient catalyst for reactions involving a lot of complexity is always a challenge for catalyst researcher. Methane to methanol, CO2 conversion to hydrocarbons, aromatization of LPG, biomass to chemicals and fuels, aerobic oxidations are some examples which pose a challenge till today to design efficient catalysts for these reactions.

  1. Catalyst design for biofuel synthesis

    The research in the present decade is mainly dedicated to “energy” because of the concerns over diminishing fossil fuels like LPG, petrol and diesel. A lot of efforts are going on to make new biofuels from renewable sources such as non-edible vegetable oils, wet biomass and wood based biomass. Biodiesel synthesized from catalytic transesterification of vegetable oilwas already tested to be fit to use as a blend with diesel. Biomass processing with multiple steps like hydropyrolysis and gasificationyields mixture of hydrocarbons and oxygenated compounds which upon refining can yield biofuels with desired quality. However, easier said than done, it is a challenge to design catalysts to selectively produce the desired biofuels with high efficiency.

  2. Novel catalytic materials

    There are many reactions for which existing catalysts have some drawbacks and could not give good efficiency for required products. Also, there are many reactions for which homogeneous catalysts are used till today and need to be replaced with heterogeneous catalysts. Catalysis research is never stagnant and requires constant efforts to find new catalysts better than existing ones. New materials always open up a lot of research to study their unknown properties.

  3. Chemical fixation of CO2 by converting into valuable chemicals.

    Industrial and automobile effluent gas, CO2 conversion to hydrocarbons over catalysts has been shown very little research and development attention so far, as other technologies has been much cheaper and efficient in yielding hydrocarbons. However, nowadays, with the increasing awareness of the impact CO2 is having on the environment,a lot of attention is being directed at the methods to mitigate the effects CO2 as a greenhouse gas.Electricity generation from coal flue gas from chemical industries and running automobiles contribute to a great extent in generating CO2. Hence it is necessary to convert CO2 from industrial flue gas into valuable chemicals instead of leaving it into atmosphere. However, CO2 being an inert gas, its activation and conversion into valuable chemicals is a challenge and require a design of catalyst to make these processes feasible.

Pore engineering of micro porous materials for shape-selective organic transformations

Vapor phase alkylation and disproportionation of aromatics are important reactions practiced in petrochemical industries. For these reactions, thermodynamic equilibrium mixtures of all the regioisomers are obtained with non-selective catalyst. Selectivity towards para-isomer can only be increased by the application of shape-selective catalyst. The para-isomer being commercially important than the other two for many organic reactions, post synthesis modification is desirable to improve the product selectivity. Zeolites are known as shape-selective catalysts due to the presence of micropores with pore diameter close to the molecular diameter of the products. However, pore modification is essential for substantially improving the shape selectivity towards a particular product. Post synthesis modification has been carried out by silanation, selective coking and metal/non-metaloxide impregnation. Phosphate modification was studied extensively by our group to explore the generation of new active sites, correlation of shape selectivity with phosphate modification and several model reactions such as toluene alkylation, ethyl benzene ethylation and disproportionation and competitive reaction of meta xylene and ethyl benzene. Two of such works are published in Applied Catalysis A journal.

Research on novel catalytic materials

There has been an increasing interest in recent years in developing novel heterogeneous catalysts for the selective synthesis of fine and specialty chemicals. In such attempt, our group studied extensively several materials and able to discover two materials as solid acid and base catalysts for the first time. Both studies have been published in reputed RSC Advances journal. Metal hydroxychlorides are well known as minerals found in various parts of the world. One such example is tin(II)hydroxychloride, a mineral known by the name abhurite. The crystallographic and mineralogical properties oftin(II)hydroxychloride are well understood but its application has been overlooked so far. Its insolubility in water and organic solvents stimulated our curiosity to study its properties and application as a heterogeneous catalyst for Prins reaction.

 

In another study, zinc hydroxystannate (ZnSn(OH)6) has been reported for the rst time as a solid bifunctional catalyst and has been applied for the synthesis of Glycerol carbonate from glycerol and urea. It has a perovskite type crystal structure with metal atoms octahedrally coordinated with corner sharing hydroxyl groups to form Sn(OH)6 and Zn(OH)6octahedra. We found that it has a strong basicity along with Lewis acidic Zn which makes it a bifunctionalheterogeneous catalyst. Its applications in other organic transformations are under progress.

Designing catalysts for biofuel synthesis

Increasing demand for petroleum fuels and depleting availability of crude oil has made to look for alternative sources of energy. The major challenge for scientific community is to develop a technology compatible with the existing source in terms of quality with an affordable price. Biodiesel is one such source which attracted many researchers since it can be easily synthesized by transesterification of vegetable oil with alcohol in presence of an acid or base catalyst. The widely known homogeneous base catalysts used since many years are NaOH and KOH because of their activity and affordable price. However, a lot of issues like difficulty in separation of catalyst from the product, contamination of the product by alkali, generation of excess waste water during product purification, environmental problems in catalyst disposal and corrosion of reactor were observed. To overcome all these issues, heterogeneous catalysts are beingdeveloped to make biodiesel synthesis, an eco-friendly process. Such a study to make a novel and efficient catalyst for biodiesel synthesis is under progress.

Catalytic conversion of waste bioglycerol from biorefinery to value-added chemicals

Glycerl is obtained as a byproduct during transesterification of vegetable oil which accounts for one tenth of every gallon of biodiesel produced. Increasing availability of glycerol has made it an inexpensive and abundant raw material to synthesize value-added chemicals and hence it is a challenge for researchers to utilize this waste glycerol to transform into commercially important products.The major direct utilities of this compound are in cosmetics, personal care products and soaps. However, these sectors may not be able to consume tons of glycerol produced from biodiesel plants.Moreover, it is well known that glycerol can be converted into chemicals by catalytic processes namely,acetalization, oxidation, hydrogenation, esterification, etherification,transesterification, dehydration, oligomerization and pyrolysis. Hence, there is a greatcommercial interest to design green and chemoselective catalysts for these processes. Our group has reported KF/alumina, metal hydroxystannate and zeolite beta catalysts for transeterification, carbonylation and acetalyzation reactions respectively which published in reputed international journals viz. Catalysis Letters, RSC Advances and Journal of Molecular Catalysis A.

  1. “Enhancement in activity and shape selectivity of zeolite BEA by phosphate treatment for 2- methoxynaphthalene acylation”, Janardhan L. Hodala, Anand B. Halgeri and Ganapati V. Shanbhag, RSC Advances, Volume 6, (2016),90579–90586
  2. “Aromatization of C5-rich Light Naphtha Feedstock over Tailored Zeolite Catalysts: Comparison with Model Compounds (n-C5 - n-C7)”, Janardhan L. Hodala,Anand B. Halgeri,Ganapati V. Shanbhag,*R. Sudarshan Reddy,Nettem V. Choudary,Peddy V.C. Rao, Mr. GandhamSriGanesh,Gitesh Shahand Raman Ravishankar*, ChemistrySelect (Wiley), Volume 1, (2016), 2515 – 2521

  3. “The Synthesis of biodiesel and acetins by transesterification reactions using novel CaSn(OH)6 heterogeneous base catalyst, catalyst” S. Sandesh, P. R. Kristachar, P. Manjunathan, A. B. Halgeri, G. V. Shanbhag*, Applied Catalysis A: General (Elsevier), Volume 523 (2016) 1–11

  4. “Catalytic etherification of glycerol to tert-butyl glycerol ethers using tert-butanol over sulfonic acid functionalized mesoporous polymer, Pandian Manjunathan, Manish Kumar, Sathyapal R Churipard, S Sivasankaran, Ganapati V Shanbhag, Sanjeev P Maradur”, RSC Advances, Volume 6, (2016), 82654-82660

  5. “Novel bifunctional Zn–Sn composite oxide catalyst for the selective synthesis of glycerol carbonate by carbonylation of glycerol with urea” Manjunathan P., Ravishankar R., and Shanbhag G. V*.; ChemCatChem,  Volume 8, (2016), 631 – 639

  6. “Superior performance of mesoporous tin oxide over nano and bulk forms in the activation of a carbonyl group: conversion of bio-renewable feedstock”, Marakatti V. S., Manjunathan P., Halgeri A. B. , Shanbhag G. V.*; Catalysis Science & Technology (RSC, London), Volume 6, (2016), 2268–2279.

  7. Glycerol acetins: fuel additive synthesis by acetylation and esterification of glycerol using cesium phosphotungstate catalyst, Swetha Sandesh, Pandian Manjunathan, Anand B. Halgeri and Ganapati V. Shanbhag*, RSC Advances, Volume 5, (2015),104354.

  8. Molybdenum oxide/γ-alumina: an efficient solid acid catalyst for the synthesis of nopol by Prins reaction, Vijaykumar S. Marakatti, Dundappa Mumbaraddi, Ganapati V. Shanbhag, Anand B. Halgeri and Sanjeev P. Maradur, RSC Advances, Volume 5, (2015), 93452–93462

  9. “Green and Sustainable Tandem Catalytic Approach for Fine- Chemicals Synthesis Using Octahedral MnO2 Molecular Sieve: Catalytic Activity versus Method of Catalyst Synthesis”, Bhaskar Sarmah,Rajendra Srivastava,Pandian Manjunathan,and Ganapati V. Shanbhag, ACS Sustainable Chemistry & Engineering, Volume 3, (2015), 2933−2943

  10. “Shape-selective synthesis of para-diethylbenzene over pore-engineered ZSM-5: a Kinetic study”Janardhan L. Hodala, Yajnavalkya S. Bhat, Anand B. Halgeri and Ganapati V. Shanbhag*, Chemical Engineering Science (Elsevier), Volume 138(2015)396–402.

  11. "Influence of alkaline earth cation exchanged X zeolites towards ortho-selectivity in alkylation of aromatics: Hard-Soft-Acid-Base concept", Vijaykumar S. Marakatti, Peddy V. C. Rao, Nettem V. Choudary, Gandham SriGanesh, Gitesh Shah, Sanjeev P. Maradur, A B. Halgeri, Raman Ravishankar*, Ganapati V. Shanbhag*, Advanced Porous Materials (American Scientific Publishing), Volume 2, (2014), 1–9.

  12. “Utilization of renewable resources: Condensation of glycerol with acetone at room temperature catalyzed by organic–inorganic hybrid catalyst”, Swetha Sandesh, A.B. Halgeri, Ganapati V. Shanbhag*, Journal of Molecular Catalysis A: Chemical (Elsevier), Volume 401, (2015), 73-80.

Sponsored Projects:

Completed Projects as Principal Investigator:

  1. Design and development of a catalyst and process for selective alkylation of aromatics. Sponsored by GTC Technology, USA 2011-2015.
  2. Post-synthesis modification and surface treatment of some solid catalysts
  3. Sponsored by Shell Techonology Centre, Bangalore 2012-2013.
  4. Development of Zeolite Modifed Catalysts for the Hydrocarbon Conversions
  5. Sponsored by: HPCL R&D Centre, Bangalore, 2012-2014.

 

Ongoing Projects as Principal Investigator:

  1. Design and development of a catalyst and process for selective alkylation of aromatics. Sponsored by GTC Technology, USA 2017 (continued)
  2. Design and development of a catalyst and process for natural gas and LPG conversion into alkenes and aromatics. Sponsored by PW Technology Inc, USA 2016- 2017.
  3. Development of Novel Solid Catalysts for Light Naphtha Valorization
  4. Sponsored by: HPCL R&D Centre, Bangalore, 2015-2017.
  5. Chemical fixation of CO2 into value added products using metal modified ordered nanoporous silicate catalysts, Sponsored by Vision Group of Science and Technology (VGST), Govt of Karnataka in under the category, “Centre of Excellence in Science Engineering and Medicine” (CESEM) for 2014-2017.

 

Academic Projects:

  1. Pore engineering of ZSM-5 zeolite by phosphorous oxide modification for the shape selective synthesis of p-diethylbenzene (PDEB) by alkylation of ethylbenzene with ethanol.
  2. Design and development of eco-friendly novel solid base catalysts for the transesterification of non-edible oils to produce biodiesel.
  3. Utilization of chemicals from biorefinery: Conversion of bioglycerol and furfural to value-added products.
  4. A novel heterogeneous solid acid catalysts for the synthesis of nopol and dioxanes from Prins reaction.
  5. Design of solid bifuntional catalysts for CO2 transformation into cyclic carbonates by carbonylation of epoxides
  6. Novel solid acid-base catalysts for important organic transformations.
  • 2010-Present: Asst. Professor, PPISR, Bangalore, India

  • 2008-2010: Research Scientist, Dept. of Chemistry, Korea Advanced Institute of Science and technology (KAIST), South Korea

  • 2002-2008: Ph.D. National Chemical Laboratory, Pune India (Degree by University of Pune)
  • 2000-2001: Research Associate, ICI India Ltd (MNC), Mumbai, India
  • 1999-2000: Lecturer, M.M Arts and Science College, Sirsi, Karnataka, India
  • 1999: M.Sc. Organic Chemistry, Karnatak University, Dharwad, India
  • Recognized PhD guide from Manipal University, Karnataka
  • Total publications/book chapters/patents: 41
  • Current H-Index (Scopus database): 15
  • Papers presented in conferences and symposiums: 10
  • Invited talks:  07
  • Number of PhDs guided : 02
  • Number of PhDs as co-guide: 01
  • Number of M.Tech thesis guided: 03
  • Total number of research fellows and project engineers in the current group: 08
  • Number of sponsored projects: 04
  • Received a Meritorious Award for Excellence in Research from AMEF during Founder’s day July 6, 2012 in recognition of contribution towards research and development at PPISR.

  • Editorial board memberof an international journal “Journal of Catalyst and Catalysis.”

  • Member of the Syllabus revision committee for Chemistry for Siddaganga Institute of Technology (SIT), Tumkur.

  • Referee for international journals: Chemical Communications, Applied Catalysis A, Catalysis Science and Technology, Catalysis Communications and Journal of Chemical Sciences etc.

  • Resource personfor Refresher Course Programme for PU college Lecturers sponsored by VGST, Govt of Karnataka.

  • Co-inventorin the 2 World patent (PCT)applications filed by HPCL R & D Centre, Bangalore evolved as a result of a collaborative project.

  • Three best oral/poster presentation awardsto the group for the research papers presented at National symposiums/workshops, 1. Kuvempu University on “Social Relevance of Chemical Sciences” in March 2011 (student: Mrs. SwethaSandesh) 2.  Manipal Institute of Technology , “National Symposium on Chemistry and Humanity” in Manipal, July, 2011 (Student: Mr. Janardhan H L) and 3. National Workshop on Catalysis, CSIR-NEERI, Nagpur, Maharashtra on 4-5, Feb 2014 (Student: Mr. VijaykumarMarakatti).

  • Received ‘plaques’ from GTC Technology Inc. USA in 2012, 2014 and 2015 in recognition of the milestonesachieved by the group in developing 1st and 2nd generation catalyst for xylene synthesis. 

Mr. Manjunathan P.

Senior Research Fellow(CSIR)

Mr. Manjunathan is working on the research topic “Designing heterogeneous catalysts for the conversion of glycerol and furfural to value added chemicals.” He is working on mixed metal oxides catalysts and mesoporous metal oxides for the synthesis of glycerol carbonate, solketal, acetals nopol and butyl levinulate.Before joining PPISR for research, he secured a first rank (Gold medal) in M.Sc. in Inorganic Chemistry at Bangalore University in 2012. He obtained CSIR-Senior Research Fellowship in 2017.

 


Mr. NagendraKulal

Research Fellow (Project)

Nagendra is doing research on “Chemical fixation of CO2 by converting into value-added chemicals using heterogeneous catalysts”. He obtained his MSc from St. Aloysius College Mangalore in 2013. Joined the group in 2015 September in VGST Sponsored CESEM project.

 


Mr. Manjunath Doddamani

Research Fellow (Project)

Manjunath Doddamani is working on Design of eco-friendly catalysts for conversion of biomass and its byproducts into valuable chemicals. He did his MSc from Rani Chennamma University, Belagavi in 2015. He initially worked in GTC USA sponsored industry project for one year before joining for a PhD programme. 

 


Mr. Abhishek Yadav

Research Fellow (Project)

Abhishek Jadhav is conducting research on Novel catalyst development for aromatization of light naphtha. He did MSc from Karnatak University, Dharawad and joined PPISR in July 2016.

 


Mr. Saikiran Malegapari

M.Tech. (Chemical Engineering)

Project Fellow: Working in the sponsored projects on catalyst development for vapour phase alkylation of aromatics, gas to liquid conversions and aromatization reactions.


Ms. Anusha R

B.Tech. (Chemical Engineering)

Project Fellow: Working in the sponsored projects on catalyst development for vapour phase alkylation of aromatics, gas to liquid conversions and aromatization reactions.

 


Ms. Vaishnavi B.J.

MSc (Chemistry)

Project Fellow: Working in the sponsored projects on catalyst development for vapour phase alkylation of aromatics, gas to liquid conversions and aromatization reactions.

 


Mr. Sujith S.

MSc(Chemistry) 

Project Fellow: Working in the sponsored projects on catalyst development for vapour phase alkylation of aromatics, gas to liquid conversions and aromatization reactions.


Alumni: Dr. Vijaykumar Marakatti

PhD on the topic: Design of solid acid catalysts for Prins reaction and toluene methylation

PhD from: Manipal University

Guide: Dr. Ganapati Shanbhag

Co-guide: Dr. A. B. Halgeri

Date of Registration for PhD: 10th December 2011

Date of Award: 28thApril 2015

Number of Publications: 08

Number of Patents: 01 (filed)

Present Position: Research Associate, JNCSAR, Bengaluru


Alumni: Dr. Janardhan H L

PhD on the topic: Studies on pore modified zeolite catalysts for aromatization and aromatic substitution reactions

PhD from: Manipal University

Guide: Dr. Ganapati Shanbhag

Co-guide: Dr. A. B. Halgeri

Date of Registration for PhD: 10th December 2011

Date of Award: 10th June, 2015

Number of Publications: 05


Alumni: Dr  Swetha Sandesh

PhD on the topic: Novel eco-friendly catalysts for biodiesel synthesis and conversion of byproduct glycerol into value-added products

PhD from: Manipal University

Guide: Dr. A. B. Halgeri

Co-guide: Dr. Ganapati Shanbhag

Date of Registration for PhD: 10th December 2011

Date of Award: 09thMay 2015

Number of Publications: 06

Present Position: CEO, Niranthara Scientific Solutions Pvt Ltd