Heterogeneous Catalysis and Catalytic Processes (CATHPRO)


Carlos Henriques

Group Coordinator: Carlos Manuel Faria de Barros Henriques

As a research group based in Heterogeneous Catalysis, CATHPRO started in the 90s, focused on Catalysis by Zeolites.
CATHPRO is currently constituted by 8 IDI, 3 PhD collaborators and 3 NIDI members (PhD students).
CATHPRO research and scientific activity is organized in five areas:

A - Synthesis and Post-synthetic Treatment and Modification of Catalysts and Adsorbents, focused on: zeolites and zeotypes
(ALPOs, SAPOs and MeAPOs); metal oxides supported on porous materials; ordered mesoporous silicas used as inorganic
supports; hierarchical materials combining micro and mesopores; mesoporous silicas-based supported catalysts for olefin
polymerization and ROP.

B - Catalysis for Energy, addressed on: catalysis for oil refining (cracking and hydrocracking), transformation of biomass
renewable feedstocks and use of CO2 as feedstock for fuels (SNG, DME) and chemicals (MeOH). A new subject, involving the
use bifunctional catalysts for the transformation of waste polymers into liquid fuels, has recently started.

C - Environmental Catalysis, mainly focused on the development of active and stable catalysts for the control of: NOx emissions
from automotive and stationary sources, as well as volatile organic compounds (VOCs) emissions.
Recently, a new subject involving the simultaneous elimination of NOx and VOCs from Municipal Waste Treatment units has

D - Catalysis for functional and nanostructured polymers, that include the production of functional polyolefins and polyesters,
nanostructured PE/UHMWPE blends and polymer nanocomposites derived from these polymer matrixes.

E - Industrial Catalytic Processes Modelling and Control of industrial plants has been applied and developed using software
packages (MATLAB, gPROMS, GAMS and FORTRAN) to the modelling, control and optimization of Refining and Petrochemical
processes, Reactive Distillation columns, modelling and simulation of Ca-Loop Cycle sorbents for CO2 capture; Wastewater
Treatment units.

It consists on the conversion of captured CO2 into Synthetic Natural Gas (SNG) using hydrogen produced by renewable electric
(RE) power sources, allowing CO2 recycling as well as the storage of RE power and grid stabilisation. It involves two sequential
steps: (i)Ca-Looping for CO2 capture: results show that natural sorbents as Dolomites and waste marble powders are promising
natural inexpensive adsorbents, due to their increased CO2 carrying capacity and better cyclic stability, when compared with
standard Ca-based sorbents such as limestone and commercial CaCO3; (ii) Catalytic methanation of CO2: optimized hybrid
zeolite-based multifunctional catalysts, used for CO2 methanation were tested under meaningful experimental conditions (TRL 4-5
was achieved). Both thermal and DBD plasma-assisted catalysis were assessed. Best catalysts present enhanced activity and
selectivity for methane, when compared with tested commercial Ni/Al2O3 catalysts.

The main objective of this study was to evaluate and understand the influence of typical oxygenated compounds, present on the
bio-oils obtained from biomass thermal treatment, on the catalytic properties of the active phases of fluid catalytic cracking (FCC)
catalysts (HY and HZSM-5 zeolites), and also of the equilibrated industrial catalyst, considering the possibility of bio-oils and
crude conventional feedstocks co-processing in the FCC process for fuel production.
In order to simulate the bio-oils co-feeding, different model O-compounds, representative of the bio-oils compositions, were mixed
with the hydrocarbon reactant, at several concentrations, such as phenol and guaiacol. Different reactant molecules were used:
the methylcyclohexane and n-heptane transformations were carried out as model reactions of catalytic cracking, representative of
the compounds classes present in the conventional FCC feedstocks: naphtenes and alkanes.

This research aims to prepare advanced polyolefin materials comprising: a) high performance polyolefin (HDPE and UHMWPE)
nanocomposites/hybrids and b) tailored reactor blends, through in situ supported ethylene polymerization on ordered mesoporous
silicas (MCM-41, SBA-15) channels. Special interactions between the mesoporous material and PE are developed under the
confined synthetic conditions. A step forward involved the use of interfacial agents, (undecenoic acid and organosilanes) aiming to
boost adhesion at organic-inorganic interfaces and to improve dispersion of MCM-41 particles within HDPE matrix. The issuing
hybrid materials show an interesting gas permeation behavior and enhanced mechanical response. Recently, multisite olefin
polymerization catalysis coupled to a suitable support, SBA-15, were used to attain disentangled UHMWPE and


Rui Bartolomeu, Bruno Azambre, Alexandre Westermann, Auguste Fernandes, Raquel Bértolo, Houeida Issa Hamoud, Carlos Henriques, Patrick Da Costa, Filipa Ribeiro, “Investigation of the nature of silver species on different Ag-containing NOx reduction catalysts: on the effect of the support”, Applied Catalysis B 150–151 (2014) 204–217. http://dx.doi.org/10.1016/j.apcatb.2013.12.021

I. Graça, L.V. González, M.C. Bacariza, A. Fernandes, C. Henriques, J.M. Lopes, M.F. Ribeiro” CO2 hydrogenation into CH4 on NiHNaUSY zeolites”, Applied Catalysis B 147 (2014) 101–110. http://dx.doi.org/10.1016/j.apcatb.2013.08.010

Ana Neto, Sébastien Thomas, Gary Bond, Frédéric Thibault-Starzyk, Filipa Ribeiro and Carlos Henriques, “The Oil Shale Transformation in the Presence of an Acidic BEA 2 Zeolite under Microwave Irradiation”, Energy Fuels 28 (2014) 2365–2377. http://dx.doi.org/10.1021/ef4023898

Mónica Silva, Auguste Fernandes, Suse S. Bebiano, Mário J. F. Calvete, M. Filipa Ribeiro, Hugh D. Burrows and Mariette M. Pereira, “Size and ability do matter! Influence of acidity and pore size on the synthesis of hindered halogenated meso-phenyl porphyrins catalysed by porous solid oxides”, Chem. Commun., 50 (2014), 6571-6573. http://dx.doi.org/10.1039/C4CC01100G

Inês Graça, José M. Lopes, Henrique S. Cerqueira and Maria F. Ribeiro, “Bio-oils Upgrading for Second Generation Biofuels” Ind. Eng. Chem. Res., 52 (2013) 275-287. http://dx.doi.org/10.1021/ie301714x

Rui Bartolomeu, Raquel Bértolo, Sandra Casale, Auguste Fernandes, Carlos Henriques, Patrick da Costa, Filipa Ribeiro, “Particular characteristics of silver species on Ag-exchanged LTL zeolite in K and H form” Microporous and Mesoporous Materials 169 (2013) 137–147. http://dx.doi.org/10.1016/j.micromeso.2012.10.015

A. Martins, J. M. Silva, M. F. Ribeiro, “Influence of rare earth elements on the acid and metal sites of Pt/HBEA catalyst for short chain n-alkane hydroisomerization” Applied Catalysis A 466 (2013) 293–299. http://dx.doi.org/10.1016/j.apcata.2013.06.043

M. L. Cerrada, E. Pérez, J. P .Lourenço, A. Bento, M. Rosário Ribeiro, “Decorated MCM-41/polyethylene hybrids: Crystalline details and viscoelastic behaviour” Polymer 54 (2013) 2611-2629. http://dx.doi.org/10.1016/j.polymer.2013.03.010

A. Bento, J. P. Lourenço, A. Fernandes, M. L. Cerrada, M. Rosário Ribeiro, “Functionalization of mesoporous MCM-41 (nano)particles: preparation methodologies, role on catalytic features and dispersion within PE nanocomposites”, ChemCatChem, 5 (2013) 966–976. http://dx.doi.org/10.1002/cctc.201200639

Domingues, L., Pinheiro, C.I.C., Oliveira, N.M.C., Fernandes, J., Vilelas, A., “Model Development and Validation of Ethyl tert-Butyl Ether Production Reactors Using Industrial Plant Data“, Industrial & Engineering Chemistry Research, 51 (2012) 15018–15031 (http://dx.doi.org/10.1021/ie302030j)