Project title

 Multi-functional core-shell magnetic nanoparticles for the direct synthesis of furan-2, 5- dicarboxylic acid (FDCA) from cellulose (NanoMagCat)

Project Code and number

PN-III-P4-ID-PCE-2016-0533; No. 116/2017

Contracting Authority

UEFISCDI

Project Host Institution

University of Bucharest

Run period

12.07.2017-31.12.2019

Total funding

850.000,00 lei



Project Summary


The recent interest for bio-plastics has raised the interest for production of organic acids as bi-functional monomers, completing their traditional uses in feed and food. Furan-2,5-dicarboxylic acid (FDCA), for instance, is a promising biomass-derived chemical with wide application in different industrial segments. Most important, since it has similar functional groups as terephtalic acid, FDCA is an extremely high potential platform chemical which can substitute for petrochemical derived terephthalic acid (PTA) in the production of polyesters and other current polymers containing aromatic moiety. Nevertheless, in spite of its huge industrial potential, FDCA is commercially (industrially) not yet produced because of the high price production.

The present project challenges the direct FDCA catalytic synthesis from renewable raw materials such as cellulose. Such concept requires the development of a cost effective and industrially viable oxidation of HMF to FDCA technology able to operate in concert with the necessary dehydration processes of cellulose to HMF. To reach the project challenge, multi-functional Me(Me=Co, Mn, Fe)@M(M= Sn, Nb)-Si@MNP core-shell magnetic nanoparticles, combining non-noble metal (Co, Mn, Fe) and acid sites (Sn(IV), Nb(V)), will be designed and developed for the one-pot synthesis of FDCA from cellulose. The flow chemistry approach by using multi-phase systems will be also designed for the best batch reactions. Moreover, an advanced integrated strategy to maximize the value of the eventually formed humins wastes to bio-fuels will be developed.


The implementation degree of the project:


Phase I/2017 (12.07.2017– 31.12.2017): Synthesis of Sn @ MNP and Nb @ MNP core-shell catalysts with high efficiency in dehydration of glucose / cellulose to HMF


In order to achieve this phase, the following activities were carried out:


Activity 1.1. - Synthesis of "core-shell" Sn@MNP and Nb@MNP catalysts

Activity 1.2. - Physico-chemical characterization of the synthesized catalysts

Activity 1.3. - Dehydration of glucose and cellulose to HMF


Summary of the research report (Phase I):


In the reported phase, "core-shell"-like Sn@MNP and Nb@MNP (“core” – magnetic nanoparticles incorporated into the MCM walls, “shell” – mesoporous silica (MCM-41 structure) doped with Sn or Nb) catalysts (in which, Si/Sn or Si/Nb ratio of 18, 22, 47 and 50 respectively) were prepared. To avoid the problems associated with the different reactivities of Sn (IV), Nb (V) and Si (IV) in solution, for the synthesis of the catalysts with a high dispersion of Sn (IV) or Nb (V) in the mesoporous silica structure Atran method was applied. This methodology leads to chemically homogeneous materials, avoiding or limiting the phase segregation processes that may occur by applying the classical sol-gel method.

The applied characterization techniques (XRD, DRIFT) showed that the prepared Nb@MNP catalytic samples contain large quantities of NbO-H (Nb(V)) species with a high dispersion, species that can be associated with strong Brønsted acid sites. Increasing the amount of niobium causes the formation of NbO-H species, as well as Nb(O, OH)x - type nano-domains, characterized by a much lower acidity than the former. The Sn samples (Sn@MNP) follow the same trend with the specification that the maximum amount of Sn (IV) that can be dispersed in the silica matrix corresponds to a Si/Sn = 22 ratio whereas, in the case of Nb samples, a maximum amount of Nb (V) which can be dispersed in the silica matrix corresponds to a Si/Nb ratio of 18. A further increase in the amount of tin or niobium over the specified ones leads to a collapse of the mesoporous structure by the formation of amorphous materials. The typical porous architecture of MCM-41 materials is only slightly altered by incorporating magnetic nanoparticles. Importantly, the existence of magnetite ensures a very simple separation of the catalysts from the reaction medium.

The main reaction products obtained in the dehydration of glucose in the presence of the catalysts prepared in this phase were: -hydroxyacids (lactic and glycolic acid), levulinic acid and 5-hydroxymethylfurfural (HMF). Moreover, large amounts of condensation products, generically called humine, were formed, which provoked not only a high decrease in HMF selectivity but also a gradual deactivation of the catalysts. An efficient method of suppressing the unwanted side reactions consisted in combining the dehydration of glucose in aqueous medium with in situ extraction of the formed HMF from the aqueous phase in an organic phase. Thus, the use of a biphasic aqueous solution of NaCl (20 wt%) / methyl isobutyl ketone (MIBK) brings the advantage of a high partition coefficient between the two immiscible phases favoring the extraction of HMF formed in water in the organic phase. In such biphasic systems, synthesis took place with 58-63% selectivity to HMF for 61-67% glucose conversion in the presence of Nb@MNP catalysts (Si/Nb = 18) and Sn@MNP (Si/Sn = 22). The catalysts are characterized by a high stability being recycled several runs without significant decreases of the glucose conversion and HMF selectivity. Similar tests with cellulose as raw material instead of glucose were also performed.


Phase II/2018 (01.01.2018-31.12.2018): Synthesis of bifunctional catalysts (Pd@zeolite beta) and Co@MNP, Fe@MNP and Mn@MNP catalysts for the humins transformation into liquid hydrocarbons and the oxidation of HMF to FCDA


In order to achieve this phase, the following activities are under way:


Activity 2.1. - Synthesis of bifunctional Pd@zeolite beta catalyst.

Activity 2.2. – Synthesis of Co@MNP, Fe@MNP and Mn@MNP catalysts

Activity 2.3. - Physico-chemical characterization of the synthesized catalysts

Activity 2.4. Oxidation of HMF to FDCA


Dissemination


Papers:


  1. M. El Fergani, N. Candu, S. M. Coman, V. I. Parvulescu, Molecules, 2017, 22(12), 2218; doi:10.3390/molecules22122218

  2. N. Candu, M. El Fergani, M. Verziu, B. Cojocaru, B, Jurca, N. Apostol, C. Teodoresu, V. I. Parvulescu, S. M. Coman, Efficient glucose dehydration to HMF onto Nb-BEA catalysts, Catal. Today, 2018, under revision

  3. A. Tirsoaga, M. El Fergani, V. I. Parvulescu, S. M. Coman: HMF upgrade to dicarboxylic acids on multifunctional based Fe3O4@SiO2 magnetic catalysts, ACS Sustain. Chem. Eng., 2018, under revision


Communications:


  1. N. Candu, S. M. Coman, V. I. Parvulescu, 9th International Symposium on Group Five Elements, 22-24 November 2017, New Delhi, India (ORAL PRESENTATION)

  2. S. M. Coman, I. Podolean, C. Rizescu, H. Garcia, V. I. Parvulescu, 27th Organic Reactions Catalysis Society Meeting, 8-12 April 2018, San Diego, CA USA (ORAL PRESENTATION)

  3. M. El Fergani, S. M. Coman, V. I. Parvulescu, Young Researchers' International Conference on Chemistry and Chemical Engineering (YRICCCE II), 3-5 May 2018, Budapest, Hungary (ORAL PRESENTATION)

  4. C. Rizescu, I. Podolean, J. Albero, V. I. Parvulescu, S. M. Coman, C. Bucur, M. Puche, H. Garcia, EFCATS School on Catalysis, 25-29 June 2018, Liblice Castle, Czech Republic (ORAL PRESENTATION)

  5. N. Candu, M. El Fergani, S. M. Coman, V. I. Parvulescu, EFCATS School on Catalysis, 25-29 June 2018, Liblice Castle, Czech Republic (ORAL PRESENTATION)