Project 151 from 2012

Extensive valorization of lignin and salicylic acid to bulk and fine chemicals

LISALCHEM

Încheiat în cadrul Program PARTENERIATE, Subprogram  Proiecte Colaborative de Cercetare Aplicativă

DIRECTIA DE CERCETARE D7: Materiale, procese si produse inovative

Project description

The present project proposes several novelties. The first one refers to the nature of the chemical compounds are intended to be produced using lignin as starting material. The second novelty refers to the nature of the catalyst will be used in this scope. On one side it should present two functionalities: acidic to disrupt oxygen bonds and to catalyze acylation and alkylation reactions, and second to hydrogenate the disrupted fragments. On the other side, the catalysts should exhibit a nano-to-micro size in order to easy penetrate inside the polymers and to present a high density of defects that are directly connected to the population of the active centers in these catalysts. The chemical composition of catalysts represents another novelty, since it should be cheap and recoverable. The fourth novelty refers to the combination of valorization of lignin with salicylic acid. Another expected novelty is the establishment of analytic methodologies. The methods proposed till now in the literature are rather contradictory


Objectives

The main objective of the project is the Extensive valorization of lignin and salicylic acid to bulk and fine chemicals. Starting from this main objective the project will consider a series of derived objectives:

  • Extraction of lignin and salycilic acid
  • Synthesis of novel heterogeneous catalysts for depolymerization of lignin and acylation/alkylation of the resulted fragments
  • Catalytic depolymerization of lignin under mild conditions coupled with catalytic acylation/alkylation of the resulted fragments
  • Synthesis of surfactants and lignans
  • Optimized conditions for catalytic depolymerization of lignin under mild conditions.
  • Optimized conditions for synthesis of surfactants and derived structures


Coordinating institution

University of Bucharest

Faculty of Chemistry

Department of Organic Chemistry, Biochemistry and Catalysis

Bd. Regina Elisabeta nr. 4-12, 030018, Bucharest, Romania


Consortium:

Name of organization involved in the project

Acronym organization

Type of organization

Organization's role in the project
(Coordinator / partner)
 

University of Bucharest

UOB

UNI

Coordinator

The Research and Development National Institute of Chemistry and Petrochemistry – ICECHIM Bucharest

ICECHIM

INCD

P1

The "C.D.Nenitzescu" Center of Organic Chemistry of the Romanian Academy

CCO

I-AR

P2

Biomass Energy Farming SRL


SRL

P3

Poll Chimic SA


SACD

P4



Contracting authority:

Unitatea Executivă pentru Finanţarea Învăţământului Superior, a Cercetării, Dezvoltării şi Inovării (UEFISCDI),

Bucureşti, Str. D. I. Mendeleev nr. 21-25, sector 1, tel 021 3023850, fax. 021 3115992, cod fiscal 12354176, cont IBAN RO83 TREZ 7015 003X XX01 1609, Trez. Sect.1, e-mail office@uefiscsdi.ro, reprezentată prin Ordonator de credite Director General Adrian CURAJ şi Contabil Şef Elena TIŢA


Duration of the project: 36 months


Implementation Plan 


-          Extraction of salycilic acid P3

-          Extraction of lignin P2

-          Cultivation of different species as raw materials for extraction P2

-          Synthesis of supports for lignin depolimerisation of lignin CO

-          Synthesis of nickel catalysts supported for lignin depolimerization CO

-          Synthesis of promoted  nickel catalysts supported for lignin depolimerization CO

-          Sinthesis of supports for acylation/alkylation catalysts P1

-          Functionalization of supports for lignans synthesis P1

-          Functionalization of supports for acylation/alkylation catalysts P2

-          Investigation of the type of the reactor and kinetics P3

-          Investigation of the solvent nature. CO

-          Selection of the heterogeneous catalyst CO

-          Diversification of energy willow hybrid culture and supplying samples for extraction CO

-          Reaction of acylation/alkylation with different agents P1

-          Determination of tensioactive properties of obtained compounds P1

-          Establishment of influence of nature of catalyst and condition of reaction P4

-          Determination of

-          Determination of the pharmacological properties of synthesized lignans P2

-          Establishing influence of the nature of the catalyst and reaction conditions P2

-          Growing and supplying quantities of biomass required pilot experiments P3

-          Dissemination of of the results obtained CO

-          Optimization of catalyst composition and structure CO

-          Development of the technology for preparation of the catalysts CO

-          Piloting the technology of preparation of the catalysts P4

-          Optimization the synthesis of catalysts CO

-          Optimization of lignin depolymerization process CO

-          Dissemination of the results obtained CO

-          Piloting of lignin depolymerization technology P4

-          Development of technology  for depolymerization of lignin CO

-          Piloting of the synthesis catalysts for acylation / alkylation lignin defragmented and synthesis of lignans P2

-          Development of technology for the synthesis of catalysts for acylation / alkylation lignin defragmented and synthesis of lignans P1

-          Optimization of synthesis catalysts for acylation / alkylation lignin defragmented and synthesis lignans P4

-          Optimizing the synthesis of lignans P2

-          Development of  technology for synthesis of surfactant P1

-          Publication of the results obtained CO

-          Piloting the technology of surfactant synthesis P4

-          Development of PhD thesis P2

-          Organizing workshops with international participation CO

-          Piloting technology for synthesis of lignans CO


Project Budget
3.337.500lei
Source 1 - The state budget: 3.000.000lei
Source 2 - from other sources (co-own): 337.500lei


Results

Preparation of plant material for analysis and extraction

Chemical characterization of plant biomass

Determination of moisture

Separation of extraction compounds

Characterization of the lignin content

The development of a method for production of lignin

Lignin extraction with supercritical CO2

Extraction of salicylic acid

Catalysts for lignin depolymerization

The synthesis of  supports of catalysts for lignin depolymerization

Preparation of iron-based nanoparticles in aqueous solution

Fe-based particles in the presence of polyethylene glycol (PEG 300)

Fe-based particles in the presence of glycerol

Fe-based nanoparticles in the presence of a fatty imidazoline (ROT 1)

Fe-based nanoparticles in the presence of triblock copolymer polyethylen polypropyleneoxide oxide (Pluronic-P123)

Nanoparticles based on Fe in glycerol

Nanoparticles based on Fe in glycerine in the presence of EMAL

Nanoparticles based on Fe in glycerine in the presence nonylphenol ethoxylate (NF4)
Preparing nanoparticles based on Sn

Nanoparticles based on SN in aqueous solution
Nanoparticles based on Sn in the presence Pluronic P123
Nanoparticles based on Sn in the presence of polyvinyl alcohol

Preparation of catalysts based on Sn powder by grinding from SnO

Preparation of catalysts based on Sn by grinding in the presence DEGMBE, starting from a powder SnO

Preparation of nanoparticles based on Mn
Nanoparticles based on the basis of the MnCl2 Mn • 4H2O
Nanoparticles based on Mn from the Mn (CH3COO) 2 • 4H2O
Nanoparticles based on Mn from the Mn (CH3COO) 2 in the presence Pluronic-P123

Preparation of a catalyst based on manganese in the presence diethylene glycol monobutylether
Preparation catalysts based on iron and manganese by co-precipitation method
Preparation phosphomolybdic acid based catalysts by grinding

The synthesis of Ni catalysts supported for lignin depolymerization
The synthesis of  promoted Ni catalyst/Support for lignin depolymerization

 

Catalysts for acylation / alkylation lignin defragmented and synthesis of lignans

Functionalization of supports for lignans synthesis  

Synthesis of Sn-MCM-41
Synthesis of Sn-UVM

Preparation of SnTf-MCM-41 catalyst and SnTF-UVM-7

 

Contact information of Project Manager

Profesor Vasile PARVULESCU telefon/fax: +40(21) 410 02 41, e-mail: vasile.parvulescu@g.unibuc.ro

 

Dissemination

  1. M. Verziu, A. Richel, R.M. Richards, V.I. Parvulescu, Catalytic depolymerization of lignin under ultrasounds conditions, 4th EuCheMS Chemistry Congress, August 26–30, 2012, Prague, Czech Republic.
  2. A. Negoi, L. Zala, J.H. Clark, R. Luque, S.M. Coman, V.I. Parvulescu, Efficient Starbons-based catalysts for biomass valorization, 244th American Chemical Society National Meeting&Exposition, Division of Environmental Chemistry, Green Chemistry and the Environment Biomass and Wastes Valorisation practices, Phyladelphia, August 19-23, 2012, USA.

 

Final results

  1. K.B.H. Finch, R.M. Richards, A.Richel, A.V. Medvedovici, N.G. Gheorghe, M. Verziu, S.M. Coman,V.I. Parvulescu, Catalytic hydroprocessing of lignin under thermal and ultrasound conditions, Catal. Today 196 (2012) 3-10.

Reporting

Fisier de tip .pdf ! 2014 

Fisier de tip .PDF ! 2016 

Scientific articles:

  1. P. Sazama, B. Wichterlova, Š. Sklenak, V.I. Parvulescu, N. Candu, G. Sadovska, J. Dedecek, P. Klein, V. Pashkova, P. Štastny, Acid and redox activity of template-free Al-rich H-BEA* and Fe-BEA* zeolites, J. Catal. 318 (2014) 22–33.
  2. K.B.H. Finch, R.M. Richards, A.Richel, A.V. Medvedovici, N.G. Gheorghe, M. Verziu, S.M. Coman,V.I. Parvulescu, Catalytic hydroprocessing of lignin under thermal and ultrasound conditions, Catal. Today 196 (2012) 3-10.
  3. I. Podolean, A. Negoi, N. Candu, M. Tudorache, V.I. Parvulescu, S.M. Coman, Cellulose Capitalization to Bio-chemicals in the Presence of Magnetic Nanoparticle Catalysts, Top. Catal. 57 (2014) 1463
  4. 6. C. Opris, B. Cojocaru, N. Gheorghe, M. Tudorache, S.M. Coman, V.I.ChemCatChem 8 (2016) 1146-1156.
  5. P. Sazama, B. Wichterlova, Š. Sklenak, V.I. Parvulescu, N. Candu, G. Sadovska, J.Dedecek, P. Klein, V. Pashkova, P. Štastny, J. Catal. 318 (2014) 22–33;
  6. I. Podolean, A. Negoi, N. Candu, M. Tudorache, V.I. Parvulescu, S.M. Coman, 57 (2014) 1463-1469Top. Catal.
  7. A. Dragu, S. Kinayyigit, E.J. García-Suárez, M. Florea, E. Stepan, S. Velea, L. Tanase, V. Collière, K. Philippot, P. Granger, V.I. Parvulescu, Appl. Catal. A: General 504 (2015) 81-91;
  8. V. Kuncser, S.M. Coman, E. Kemnitz, V.I. Parvulescu,. J. Appl. Phys. 117 (2015) 17D724-1-17D724-4;
  9. P.T. Huyen, M. Krivec, M. Kočevar, I.C. Bucur, C. Rizescu, V.I. Parvulescu, ChemCatChem 8 (2016) 1146-1156;
  10. C. Opris, B. Cojocaru, N. Gheorghe, M. Tudorache, S.M. Coman, V.I. Parvulescu, B. Duraki, F. Krumeich, J.A. van Bokhoven,, J. Catal. 339 (2016) 209-227.

 

Plenaries in International Conferences:

 

  1. V. I. PârvulescuGreen synthesis of fine-chemicals using Lewis acid / base heterogeneous catalysts, 46 Polish Annual Conference on Catalysis, Krakow, March 19-21, 2014, Poland.
  2. S.M. Coman, V.I. Parvulescu, Catalytic alternatives to fermentative methodology of the cellulose valorization to platform molecules, 3rd Indo-French Symposium “Catalysis for Sustainable and Environmental Chemistry”, Pune, India, October 29-31, 2014.

 

Oral presentations in International Conferences:

  1. M. Verziu, A. Richel, R.M. Richards, V.I. Parvulescu, Catalytic depolymerization of lignin under ultrasounds conditions, 4th EuCheMS Chemistry Congress, August 26–30, 2012, Prague, Czech Republic.
  2. A. Negoi, L. Zala, J.H. Clark, R. Luque, S.M. Coman, V.I. Parvulescu, Efficient Starbons-based catalysts for biomass valorization, 244th American Chemical Society National Meeting&Exposition, Division of Environmental Chemistry, Green Chemistry and the Environment Biomass and Wastes Valorisation practices, Phyladelphia, August 19-23, 2012, USA
  3. I. Podolean, A. Negoi, N. Candu, M. Tudorache, V.I. Parvulescu,  S. M. Coman,  The cellulose capitalization to bio-chemicals in the presence of magnetic nanoparticles catalysts, The 25th Conference of the Organic Reactions Catalysis Society (ORCA), Tucson (AZ), USA, March 2nd-6th, 2014. (ORAL PRESENTATION)
  4. I. Podolean, M. Tudorache, V.I. Parvulescu,  S. M. Coman, Ru(III)-based Magnetic Nanoparticles- A Highly Efficient Catalyst for the Selective Oxidation of Levulinic Acid to Succinic Acid, The 25th Conference of the Organic Reactions Catalysis Society (ORCA), Tucson (AZ), USA, March 2nd-6th, 2014.
  5. S.M. Coman, M. Verziu, A. Tirsoaga, B. Jurca, V.I. Parvulescu, E. Kemnitz, The cascade transformation of cellulose to lactic acid in the presence of Nb based catalysts, International Conference on Green Chemistry and Sustainable Engineering, Barcelona, Spain, July 29-31, 2014 (ORAL PRESENTATION)
  6. V.I. Parvulescu, V. Kuncser, A. Negoi, M. Tudorache, S. M. Coman, Magnetite nanoparticles as efficient supports for noble metals in the valorisation of biomass, 59th Annual Magnetism & Magnetic Materials Conference, Honolulu, Hawaii, November 3-7, 2014 (ORAL PRESENTATION).
  7. A. Dragu, S. Kinayyigit, S. M. Coman, K. Philippot, V.I. Parvulescu, Selective Pd/mesoporous carbon nanocatalysts for production of transportation fuels from waste fatty acids, 3rd International Symposium on Green Chemistry, La Rochelle, France, May 3-7, 2015 (ORAL PRESENTATION).
  8. S. Coman, I. Podolean, M. Tudorache, V. I. Parvulescu, Green Synthesis of Succinic Acid in Heterogeneous Catalysis, 11th International Conference on Renewable resources and Biorefineries, York, UK, June 3-5, 2015 (ORAL PRESENTATION).
  9. P.A. Lazaridis, A. Panteli, S.A. Karakoulia, S.M. Coman, V.I. Parvulescu, K. Triantafyllidis, Cellulose valorisation by catalytic hydrolytic hydrogenation towards sugar alcohols, Green Chemistry and the Environment Symposium, Division of Environmental Chemistry, 250th ACS National Meeting, Boston, USA, August 16–20, 2015 (ORAL PRESENTATION).
  10. C.M. Opris, M. Tudorache, V.I. Parvulescu, New Catalysts for Lignin Depolymerisation, EUROPACAT XII, Kazan, Russia,30 August - 4 September, 2015
  11. I. Podolean, S.M. Coman, V.I. Parvulescu, Synthesis of Platform Molecules from Cellulose over Bifunctional Magnetc Nanocatalysts, EUROPACAT XII, Kazan, Russia,30 August - 4 September, 2015
  12. V. I. Parvulescu, I. Podolean, P. Filip, S. M. Coman, Bio-chemicals production from starch, Green Chemical Processing of Food Supply Chain Waste:Green synthetic methodologies to transform Food Waste into Value added Chemicals workshop, 8-9th September,2015, Tallinn, Estonia (ORAL PRESENTATION).
  13. S.M. Coman, M. Verziu, A. Tirsoaga, B. Jurca, E. Kemnitz, V.I. Parvulescu, From celulose to lactic acid in the presence of Nb-based catalysts, French Conference on Catalysis-1, May 23-27th, 2016, Frejus, France (ORAL PRESENTATION).
  14. S.M. Coman, M. Verziu, A. Tirsoaga, B. Jurca, E. Kemnitz, V.I. Parvulescu, Highly active and selective Nb-based catalysts for the production of lactic acid from cellulose, 16th International Congress on Catalysis, July 3-8, 2016, Beijing, China (ORAL PRESENTATION).
  15. P. Sazama, R. Pilar, L. Mokrzycki, V.I. Parvulescu, E. Tabor, A. Vondrova, D. Kaucky, P. Klein, J. Dedecek, S. Sklenak, J. Moravkova,Enhancement of concentration and functionality of active sites in zeolite based catalysts for acid and redox catalysed reactions, 16th International Congress on Catalysis, July 3-8, 2016, Beijing, China (ORAL PRESENTATION).
  16. I. Podolean, S.M. Coman, V.I. Parvulescu, Unprecedented catalytic wet oxidation of glucose to succinic acid induced by the addition of n-butyl amine to Ru-based catalysts, International Symposium on Catalytic Conversions of Biomass (ISCCB 2016), June 27-30, 2016 Taipei (Taiwan) (ORAL PRESENTATION).

 

Pagină actualizată la 29 Noiembrie 2016.