Research progress on reuse of fluid catalytic cracking waste from oil refinery in cement-based materials

Present paper present the main results obtained in the scope of an ongoing project which aims to contribute to the valorization of a waste generated by the Portuguese oil company in construction materials. This waste is an aluminosilicate with high pozzolanic reactivity. Several different technological applications had already been tested with success both in terms of properties and compliance with the corresponding standards specifications. Namely, this project results already demonstrated that this waste can be used in traditional concrete, self-compacted concrete, mortars (renders, masonry mortar, concrete repair mortars), cement main constituent as well as alkali activated binders.

Efeito da incorporação de resíduos da indústria petrolífera na durabilidade de argamassas de reparação de estruturas de betão

Na presente dissertação, o trabalho desenvolvido teve como objetivo, a avaliação de alguns parâmetros de durabilidade de argamassas com incorporação de catalisador exausto de FCC (do inglês “Fluid Catalytic Cracking”) para serem utilizadas na reparação de estruturas de betão. O catalisador exausto de FCC é um resíduo da indústria petrolífera e o utilizado neste estudo é proveniente da refinaria da Petrogal, S.A. em Sines. A presente investigação baseou-se na preparação, e avaliação de propriedades, de duas séries distintas de argamassas: a série que se denominou “RAS” e a série que se denominou “Durabilidade”, nas quais se substituiu, parcialmente entre 5, 10 e 15%, em massa de cimento por resíduo exausto de FCC. As argamassas de ambas as séries diferenciam-se entre si, sobretudo, pela utilização de areia reativa nas argamassas da série RAS e de areia inerte no caso das argamassas da série durabilidade. Nas argamassas estudadas foram realizados ensaios no estado fresco e ensaios no estado endurecido. Os ensaios no estado fresco incluíram a determinação da consistência por espalhamento, da massa volúmica e do teor de ar. Nos ensaios no estado endurecido foram avaliadas, no caso das argamassas da série RAS a extensão da reação àlcalis-sílica e no caso das argamassas da série Durabilidade as resistências mecânicas - à flexão e à compressão, a resistência à carbonatação acelerada, o módulo de elasticidade à compressão, a absorção capilar, a permeabilidade ao oxigénio, a difusão de cloretos em regime não estacionário. O trabalho desenvolvido nesta dissertação demonstrou que a incorporação de catalisador exausto de FCC, em argamassas à base de cimento, minimiza o efeito de expansão das reações álcalis-sílica, bem como contribui para reduzir a absorção capilar e coeficiente de difusão de cloretos. No entanto, este resíduo quando incorporados em argamassas contribui para a diminuição da resistência à carbonatação acelerada e para o aumento da permeabilidade ao oxigénio.

ECO-betão com adição de resíduo da indústria petrolífera

Dissertação de natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Edificações

Incorporação de resíduo da indústria petrolífera em argamassas de cal hidráulica para a reabilitação de edifícios

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Edificações

An SEM investigation of the pozzolanic activity of a waste catalyst oil refinery

The most active phase of the fluid catalytic cracking (FCC) catalyst, used in oil refinery, is zeolite-Y which is an aluminosilicate with a high internal and external surface area responsible for its high reactivity. Waste FCC catalyst is potentially able to be reused in cement-based materials - as an additive - undergoing a pozzolanic reaction with calcium hydroxide (Ca(OH)2) formed during cement hydration [1-3]. This reaction produces additional strength-providing reaction products i.e., calcium silicate hydrate (C-S-H) and hydrous calcium aluminates (C-A-H) which exact chemical formula and structure are still unknown. Partial replacement of cement by waste FCC catalyst has two key advantages: (1) lowering of cement production with the associated pollution reduction as this industry represents one of the largest sources of man-made CO2 emissions, and (2) improving the mechanical properties and durability of cement-based materials. Despite these advantages, there is a lack of fundamental knowledge on pozzolanic reaction mechanisms as well as spatial distribution of porosity and solid phases interactions at the microstructural level and consequently their relationship with macroscopical engineering properties of catalyst/cement blends. Within this scope, backscattered electron (BSE) images acquired in a scanning electron microscope (SEM) equipped with Energy-Dispersive Spectroscopy (EDS) and by X-ray diffraction were used to investigate chemical composition of hydration products and to analyse spatial information of the microstructure of waste FCC catalyst blended cement mortars. For this purpose mortars with different levels of cement substitution by waste catalyst as well as with different hydration ages, were prepared. The waste FCC catalyst used is produced by the Portuguese refinery company Petrogal S.A.

Destruction of the tar present in syngas by combustion in porous media

The cleaning of syngas is one of the most important challenges in the development of technologies based on gasification of biomass. Tar is an undesired byproduct because, once condensed, it can cause fouling and plugging and damage the downstream equipment. Thermochemical methods for tar destruction, which include catalytic cracking and thermal cracking, are intrinsically attractive because they are energetically efficient and no movable parts are required nor byproducts are produced. The main difficulty with these methods is the tendency for tar to polymerize at high temperatures. An alternative to tar removal is the complete combustion of the syngas in a porous burner directly as it leaves the particle capture system. In this context, the main aim of this study is to evaluate the destruction of the tar present in the syngas from biomass gasification by combustion in porous media. A gas mixture was used to emulate the syngas, which included toluene as a tar surrogate. Initially, CHEMKIN was used to assess the potential of the proposed solution. The calculations revealed the complete destruction of the tar surrogate for a wide range of operating conditions and indicated that the most important reactions in the toluene conversion are C6H5CH3 + OH <-> C6H5CH2 + H2O, C6H5CH3 + OH <-> C6H4CH3 + H2O, and C6H5CH3 + O <-> OC6H4CH3 + H and that the formation of toluene can occur through C6H5CH2 + H <-> C6H5CH3. Subsequently, experimental tests were performed in a porous burner fired with pure methane and syngas for two equivalence ratios and three flow velocities. In these tests, the toluene concentration in the syngas varied from 50 to 200 g/Nm(3). In line with the CHEMKIN calculations, the results revealed that toluene was almost completely destroyed for all tested conditions and that the process did not affect the performance of the porous burner regarding the emissions of CO, hydrocarbons, and NOx.

Pozzolanic activity of oil-refining catalyst: evaluation by electron and atomic microscopy

The reuse of waste fluid catalytic cracking (FCC) catalyst as partial surrogate for cement can reduce the environmental impact of both the oil-refinery and cement production industries [1,2]. FCC catalysts can be considered as pozzolanic materials since in the presence of water they tend to chemically react with calcium hydroxide to produce compounds possessing cementitious properties [3,4]. In addition, partial replacement of cement with FCC catalysts can enhance the performance of pastes and mortars, namely by improving their compressive strength [5,6]. In the present work the reaction of waste FCC catalyst with Ca(OH)2 has been investigated after a curing time of 28 days by scanning electron microscopy (SEM) with electron backscattered signal (BSE) combined with X-ray energy dispersive spectroscopy (EDS) carried out with a JEOL JSM 7001F instrument operated at 15 kV coupled to an INCA pentaFetx3 Oxford spectrometer. The polished cross-sections of FCC particles embedded in resin have also been evaluated by atomic force microscopy (AFM) in contact mode (CM) using a NanoSurf EasyScan 2 instrument. The SEM/EDS results revealed that an inward migration of Ca occurred during the reaction. A weaker outward migration of Si and Al was also apparent (Fig. 1). The migration of Ca was not homogeneous and tended to follow high-diffusivity paths within the porous waste FCC catalyst particles. The present study suggests that the porosity of waste FCC catalysts is key for the migration/reaction of Ca from the surrounding matrix, playing an important role in the pozzolanic activity of the system. The topography images and surface roughness parameters obtained by atomic force microscopy can be used to infer the local porosity in waste FCC catalyst particles (Fig. 2).

Modification of MOR by desilication treatments: Structural, textural and acidic characterization

The effect of several desilication experimental parameters (base concentration, temperature and time) on the characteristics of MOR zeolite was studied. The samples were characterized by X-ray diffraction, Al-27 and Si-29 MAS-NMR, chemical analysis, and FTIR (framework vibration region). The textural characterization was made by N-2 adsorption and the acidity was evaluated by pyridine adsorption followed by FTIR and by the catalytic model reaction of n-heptane cracking. The alkaline treatments promoted the Si extraction from the zeolite framework, without considerable loss of crystallinity and, as it was envisaged, an important increase of the mesoporous structure was attained. A linear correlation between the number of framework Si per unit cell. N-Si and the asymmetric stretching wavenumber, nu(i), was observed. The acidity characterization shows that the desilicated samples exhibit practically the same acid properties than the parent HMOR zeolite. The optimum desilication conditions were those used to obtain sample M/0.2/85/2, i.e., sample treated with 0.2 M NaOH solution at 85 degrees C for 2 h.

Hydroisomerization of n-decane over SAPO-11 catalysts synthesized with methylamine as co-template

The present work deals with preliminary studies concerning a new synthesis approach to prepare SAPO materials with AEL structure and evaluate their catalytic behavior in the hydroisomerization of long paraffins. The new SAPO-11 catalysts were synthesized with the help of a small amine (methylamine, MA) added during the preparation of the initial gel. As MA incorporates into the structure of the final materials, it contributes, together with DPA (dipropylamine), to an increase in Si incorporation as isolated species, which results in Bronsted acid sites. Thus, this new and original synthesis strategy allows to obtain materials with enhanced Bronsted acidity when compared with free MA materials. The catalysts were tested in n-decane hydroisomerization (n-decane was used as a model molecule) and confirmed the effect of MA on the acidic properties of the catalysts. The samples synthesized with MA present a higher number of acid sites that increase the catalytic conversion but have a negative effect in the isomerization selectivity, i.e. a more significant amount of cracking products is formed.

Low-Carbon Cement with Waste Oil-Cracking Catalyst Incorporation

The present paper shows preliminary results of an ongoing project which one of the goals is to investigate the viability of using waste FCC catalyst (wFCC), originated from Portuguese oil refinery, to produce low carbon blended cements. For this purpose, four blended cements were produced by substituting cement CEM I 42.5R up to 20% (w/w) by waste FCC catalyst. Initial and final setting times, consistency of standard paste, soundness and compressive strengths after 2, 7 and 28 days were measured. It was observed that the wFCC blended cements developed similar strength, at 28 days, compared to the reference cement, CEM I 42.5R. Moreover, cements with waste FCC catalyst incorporation up to 15% w/w meet European Standard EN 197-1 specifications for CEM II/A type cement, in the 42.5R strength class.

Catalytic combustion of toluene on Pt zeolite coated cordierite foams

The catalytic properties of Pt based cordierite foam catalysts have been evaluated in catalytic combustion of toluene (800 ppm in air). The catalysts contain identical Pt content (0.1%) which was introduced by three different ways: Pt ion exchange on MFI zeolite and then coating on the foam; Pt ion exchange after zeolite coating and finally Pt directly wet impregnated on the cordierite foam. The catalytic behaviour of Pt foam based catalysts was compared with that of PtMFI zeolite under powder form. Pt exchanged MFI supported on the cordierite foams present an improvement of activity for toluene combustion of about 50 degrees C on the light off temperature (T-50%). The enhanced performance of the structured catalysts is due not only to the open structure of foams and homogeneous thin layers catalyst deposited on their cell walls, but also to the fact that the size and location of Pt particles present in MFI zeolite are changed during the dipping step. Indeed, as prepared Pt samples and those used in the preparation of the slurry were observed by transmission electron microscopy revealing that the chemical interaction of PtMFI zeolite with the binder and detergent, both present in the slurry, leads to an increase of Pt particles size which were found to migrate from internal pores to the external surface of zeolite crystallites thereby increasing catalytic activity. (C) 2011 Elsevier B.V. All rights reserved.

Complexes of copper(II) with 3-(ortho-substituted phenylhydrazo)pentane-2,4-diones: syntheses,properties and catalytic activity for cyclohexane oxidation

Reactions of copper(II) with 3-phenylhydrazopentane-2,4-diones X-2-C6H4-NHN = C{C(= O)CH3}(2) bearing a substituent in the ortho-position [X = OH (H2L1) 1, AsO3H2 (H3L2) 2, Cl (HL3) 3, SO3H (H2L4) 4, COOCH3 (HL5) 5, COOH (H2L6) 6, NO2 (HL7) 7 or H (HL8) 8] lead to a variety of complexes including the monomeric [CuL4(H2O)(2)]center dot H2O 10, [CuL4(H2O)(2)] 11 and [Cu(HL4)(2)(H2O)(4)] 12, the dimeric [Cu-2(H2O)(2)(mu-HL2)(2)] 9 and the polymeric [Cu(mu-L-6)](n)] 13 ones, often bearing two fused six-membered metallacycles. Complexes 10-12 can interconvert, depending on pH and temperature, whereas the Cu(II) reactions with 4 in the presence of cyanoguanidine or imidazole (im) afford the monomeric compound [Cu(H2O)(4){NCNC(NH2)(2)}(2)](HL4)(2)center dot 6H(2)O 14 and the heteroligand polymer [Cu(mu-L-4)(im)](n) 15, respectively. The compounds were characterized by single crystal X-ray diffraction (complexes), electrochemical and thermogravimetric studies, as well as elemental analysis, IR, H-1 and C-13 NMR spectroscopies (diones) and ESI-MS. The effects of the substituents in 1-8 on the HOMO-LUMO gap and the relative stability of the model compounds [Cu(OH)(L-8)(H2O)]center dot H2O, [Cu(L-1)(H2O)(2)]center dot H2O and [Cu(L-4)(H2O)(2)]center dot H2O are discussed on the basis of DFT calculations that show the stabilization follows the order: two fused 6-membered > two fused 6-membered/5-membered > one 6-membered metallacycles. Complexes 9, 10, 12 and 13 act as catalyst precursors for the peroxidative oxidation (with H2O2) of cyclohexane to cyclohexanol and cyclohexanone, in MeCN/H2O (total yields of ca. 20% with TONs up to 566), under mild conditions.

Efeito da moagem do catalisador exausto de cracking catalítico nas propriedade de argamassas de cimento

Atualmente, o impacto ambiental gerado pela produção de cimento é uma das grandes preocupações a nível mundial. O seu processo de produção requer não só a utilização de quantidades significativas de recursos naturais não renováveis bem como de consumo de energia. Concomitantemente, a produção de cimento é a maior fonte de emissão antropogénica de CO2 para a atmosfera. Desta forma, várias medidas têm sido concebidas com o intuito de diminuir estes impactos visando a preservação do meio ambiente. Uma dessas medidas consiste em substituir parcialmente cimento por resíduos industriais. Neste sentido, com o presente trabalho pretendeu-se avaliar o efeito da moagem do catalisador exausto da unidade de “cracking” catalítico (FCC) - proveniente da refinaria da GALP, em Sines - nas propriedades de argamassas em que este resíduo substitui parcialmente o cimento. Na campanha experimental prepararam-se argamassas com substituição parcial de cimento por resíduo de FCC – entre os 0 a 15%, em massa – com três distribuições de tamanho de partículas de resíduo distintas. Na preparação destas argamassas adotaram-se duas abordagens experimentais que originaram duas séries de argamassas: numa das séries, a consistência das argamassas no estado fresco varia em função do teor de catalisador incorporado e na outra série, a consistência das argamassas é mantida constante através da adição de superplastificante, independentemente do teor de catalisador incorporado. As propriedades das argamassas no estado fresco avaliadas foram: a consistência por espalhamento, o teor de ar e a massa volúmica. No estado endurecido avaliou-se: a velocidade de propagação de ondas ultrassónicas nas argamassas, a resistência mecânica, a aderência e a absorção de água por capilaridade. Com o presente estudo verifica-se que a utilização de resíduo moído como substituto parcial do cimento, aumenta a trabalhabilidade da argamassa para substituições de 15%. Para substituições de 5% e 10%, a moagem do resíduo não se apresenta sensível à trabalhabilidade. A moagem deste resíduo de FCC também não tem um efeito significativo nos valores de resistência à compressão das argamassas em que é incorporado, embora se verifique uma tendência para que os resíduos moídos conduzam a valores resistência à compressão mais elevados quando comparado com o não moído, particularmente quando a percentagem de incorporação do resíduo é mais elevada. A atividade pozolânica aumenta com a moagem do resíduo de FCC. A introdução de resíduo moído conduz à diminuição da absorção de água por capilaridade, à medida que a percentagem de substituição aumenta.

Catalytic behavior of alkali-treated Pt/HMOR n-hexane hydroisomerization

Bifunctional Pt-HMOR catalysts were prepared by incipient wetness impregnation of various desilicated MOR obtained by alkaline treatment using NaOH concentrations ranging from 0.1 to 0.5 M. The zeolite structural changes upon modification were investigated by several techniques including powder X-ray diffraction,Al-27 and Si-29 MAS-NMR spectroscopy, N-2 adsorption, pyridine adsorption followed by infrared spectroscopy and the catalytic model reaction of m-xylene transformation. For low alkaline concentration the zeolite acidity is preserved, along with a slight increase of the volume correspondent to the larger micropores due to the removal of extra-framework debris already existent at the parent zeolite. At higher NaOH concentrations there is a significant loss of crystalinity and acidity as well as the formation of mesoporosity. The characterization of the metal function shows similar patterns for Pt-HMOR and Pt-M/0.1 samples, with Pt particles located mainly inside the inner porosity. In contrast, large Pt particles become visible at the intercrystalline mesoporosity of MOR crystals developed during the desilication treatments at severe alkaline conditions. The catalytic results obtained for n-hexane hydroisomerization showed an improved selectivity for dibranched over monobranched isomers for Pt-M/0.1 sample, likely due to the preservation of the support acidity and the slight enlargement of the micropores. This work is a new example in which the mesoporous development does not improve the catalytic efficiency of the zeolites, whereas mild alkaline desilication might be considered as an effective solution to produce customized catalysts with enhanced performance for a given application. (C) 2014 Elsevier B.V. All rights reserved.

Copper-organic frameworks assembled from in situ generated 5-(4-pyridyl) tetrazole building blocks: synthesis, structural features, topological analysis and catalytic oxidation of alcohols

Two new metal- organic compounds {[Cu-3(mu(3)-4-(p)tz)(4)(mu(2)-N-3)(2)(DMF)(2)](DMF)(2)}(n) (1) and {[Cu(4ptz) (2)(H2O)(2)]}(n) (2) {4-ptz = 5-(4-pyridyl)tetrazolate} with 3D and 2D coordination networks, respectively, have been synthesized while studying the effect of reaction conditions on the coordination modes of 4-pytz by employing the [2 + 3] cycloaddition as a tool for generating in situ the 5-substituted tetrazole ligands from 4-pyridinecarbonitrile and NaN3 in the presence of a copper(II) salt. The obtained compounds have been structurally characterized and the topological analysis of 1 discloses a topologically unique trinodal 3,5,6-connected 3D network which, upon further simplification, results in a uninodal 8-connected underlying net with the bcu (body centred cubic) topology driven by the [Cu-3(mu(2)-N-3)(2)] cluster nodes and mu(3)-4-ptz linkers. In contrast, the 2D metal-organic network in 2 has been classified as a uninodal 4-connected underlying net with the sql [Shubnikov tetragonal plane net] topology assembled from the Cu nodes and mu(2)-4-ptz linkers. The catalytic investigations disclosed that 1 and 2 act as active catalyst precursors towards the microwave-assisted homogeneous oxidation of secondary alcohols (1-phenylethanol, cyclohexanol, 2-hexanol, 3-hexanol, 2-octanol and 3-octanol) with tert-butylhydroperoxide, leading to the yields of the corresponding ketones up to 86% (TOF = 430 h(-1)) and 58% (TOF = 290 h(-1)) in the oxidation of 1-phenylethanol and cyclohexanol, respectively, after 1 h under low power ( 10 W) microwave irradiation, and in the absence of any added solvent or additive.