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 by a modified Atran method.

Different characterization techniques were applied in order to study the structure and composition of the obtained materials. Accordingly to this, bi-functional materials, comprising residual framework Al-acid sites, extra-framework isolated Nb(V) sites which correspond to Nb(V)O-H species (associated with strong Brønsted acid sites), where niobium is linked by Nb-OSi bonds to the zeolitic walls, and Nb2O5 pore-encapsulated clusters were produced after the post-synthetic insertion of Nb in the zeolite matrix. 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: α-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 / 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.


Dissemination


Papers:

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


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)



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 were carried out:

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


Summary of the research report (Phase II):


In the reported phase Co@MNP, Fe@MNP and Mn@MNP catalysts were prepared following a procedure in three steps: a. synthesis of magnetite nanoparticles by co-precipitation, b. covering of magnetite with a silica shell by sol-gel method, and c. deposition of Co, Fe or Mn oxide particles by precipitation-deposition method. For each kind of material, catalysts with 1, 5 and 10 % heteroatomic oxide were prepared. The prepared catalysts were characterized by using different techniques in order to study the structure and composition of the obtained materials. Briefly, for low concentrations of MOx (M = Mn, Co and Fe, 1-5wt%) the incorporated heteroatomic oxides are homogeneously highly dispersed on the silica shell. However, at high concentrations (ie, 10wt%) different phases of MnOx and CoOx were evidenced in XRD patterns, as akhtenskite (ε-MnO2), Mn3O4, and Co3O4 species.

In monophasic solvent (ie, water) and in the presence of a base (ie, NaOH or n-butylamine) the HMF oxidation lead to three important reaction products, in different proportions, as a function of the catalyst nature and reaction conditions, namely succinic acid (SA), maleic acid (MAc) and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA, intermediate to FDCA). All the investigated catalysts showed very good stability (ICP-OES analysis). In biphasic aqueous solution of NaCl / methyl isobutyl ketone (MIBK) system FDCA was obtained from moderate to high yields, as a function of the catalyst nature and reaction conditions.

Apart from magnetite based samples, bifunctional Pd@zeolite beta catalysts, with 0.5wt% and 1.0wt% Pd were also prepared and characterized. The catalytic tests of these catalysts in the hydrodeoxygenation reaction of water-soluble humines (formed both in the synthesis and oxidation reaction of HMF) will be carried out in Phase III of the project, according to the project's realization plan.


Dissemination


Papers:


     1. N. Candu, M. El Fergani, M. Verziu, B. Cojocaru, B. Jurca, N. Apostol, C. Teodoresu, V. I. Parvulescu, S. M. Coman, 2018, DOI: https://doi.org/10.1016/j.cattod.2018.08.04

  1. A. Tirsoaga, M. El Fergani, V. I. Parvulescu, S. M. Coman, ACS Sustain. Chem. Eng., 2018, 6(11), 14292-14301


Communications:


1. 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)

2. 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)

3. 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)

4. 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)

5. E. Kemnitz, V. I. Parvulescu, S. M. Coman, 14th Pannonian International Symposium on Catalysis, Starý Smokovec, 3 – 7 September, 2018, Slovacia (KEYNOTE LECTURE)