Fluid catalytic cracking catalyst residue (FC3R): An excellent mineral by-product for improving early-strength development of cement mixtures

doi:10.1016/S0008-8846(99)00164-7

Cement and Concrete Research

Volume 29, Issue 11, November 1999, Pages 1773-1779

https://doi.org/10.1016/S0008-8846(99)00164-7 Get rights and content

Abstract

A “new” industrial by-product obtained from the fluid catalytic cracking (FCC) process in petrol refinery is studied for construction uses. This by-product, named as fluid catalytic cracking catalyst residue (FC3R), is composed of original spherically shape particles and fragments produced in the catalytic process (30–0.1 μm) that present highly irregular morphologies. FC3R presented a very high specific surface area that produced a decrease in workability of cement-based mortars containing FC3R. Workability of FC3R-cement mortars can be increased using a superplasticizer. Replacement of cement by ground FC3R in mortars produced a very important increase in compressive strength that exceeds plain cement mortar, probably due to pozzolanic reaction. Ground FC3R can be used for preparing cements with excellent mechanical properties.

Introduction

Extensive investigations on the use of mineral admixtures in Portland cement mixtures have been carried out 1, 2, 3, 4, 5, 6. Natural and artificial mineral admixtures have been used (e.g., low-calcium and high-calcium fly ashes, silica fume, blast furnace slag, steel slag, copper, nickel and magnesium slags, volcanic ashes, diatomaceous earth, opaline rock, rice husk ash, phosphogypsum, titanogypsum, municipal solid waste incineration residues, fluid gas desulphurization residues, mining and quarrying wastes, and demolition wastes). Some of these materials are active mineral products possessing pozzolanic activity or/and cementicious properties.

The reuse of industrial by-products in concrete production offers many benefits such as: (1) environmental benefits from diminution of natural resource mining, prevention of disposal problems, energy saving, and reduction of carbon dioxide emissions; (2) economic benefits because by-products may be low-cost materials and they can be used to replace higher-cost materials and significant refuse costs can be avoided; and (3) technological advantages, improving several properties of fresh and hardened mortars and concretes, as early and long-term strength development, sulphate resistance, and rheologic properties.

Petroleum industries and particularly petrol refineries obtain specific or selected molecular-weight fractions using fluid catalytic cracking (FCC) processes. Frequently, used catalyst consists of inorganic silica-alumina-based compounds with “very open” atomic structures (zeolite type). The catalytic activity of these products has a short lifetime and the “old inactive” catalyst may be replaced by the “new active” catalyst. Thus, significant quantities of fluid catalytic cracking catalyst residue (FC3R) are produced, causing waste disposal problems. Several attempts at reuse of this residue in ceramic industry [7] in replacing kaolin as a raw material in the preparation of ceramic frits are underway.

Chemical composition and atomic structure of FC3R may be appropriate for use in mortar and concrete production. To the best of our knowledge, the first reference concerning the use of FC3R in cement and concrete production appeared in 1997 [8]. Recently, Pacewska et al. have studied some properties of cement pastes containing a spent catalyst from catalytic cracking in a fluidized bed [9].

The present paper describes preliminary and recent results on the possibility of use of FC3R in mortar production and the contribution of this “new” mineral admixture to strength development of mortars.

Section snippets

Methods

The source of FC3R was BP-Oil España S.A. refinery in Castellón (Spain). The color of the material was white or very slightly grey. Chemical composition of FC3R is given in Table 1. Analytical-grade toluene (Panreac) was used for specific gravity determination. A laboratory ball mill (Gabbrielli Mill-2) was used for grinding FC3R: 300 g of original FC3R were introduced into the bottle-mill containing 98 balls of alumina (18 mm diameter). A melamine-based product (Melcrete M-200) was used as

General characteristics of FC3R

FCC catalyst used in petroleum cracking process contains largely spherical or spheroidal shape particles (Fig. 1a), ranging from 100 to 20 μm in diameter. However, when this material is removed after use, the particle size has been significantly altered. Thus, FC3R is composed of original spherical particles and their fragments (ranging in size from 30 to 0.1 μm) that had highly irregular morphologies (Fig. 1b). FC3R particles showed a very porous appearance as the microphotographs in Fig. 1c

Conclusions

1.
Workability of mortars containing cement-FC3R mixtures is lower compared to cement plain mortar. The main reason for this behaviour is the extremely high specific surface area presented by FC3R that produces high water absorption.
2.
Grinding enhances pozzolanic properties of FC3R. Rc increases with grinding time up to 20 min; higher grinding times do not produce significant increases. All the mortars containing FC3R gave Rc higher than plain mortar except for nonmechanically treated mineral

Acknowledgements

This work was supported by BP Oil España S.A. Thanks are given to Manuel Planes (technician in charge of the Electron Microscopy Services of the Polytechnic University of Valencia).

References (11)

A. Escardino et al.
Utilizing the used catalyst from refinery FCC units as a substitute for kaolin in formulating ceramic frits
Waste Management & Research
(1995)
B. Pacewska et al.
Use of spent catalyst from catalytic cracking in fluidized bed as a new concrete additive
Thermochimica Acta
(1998)
J. Payá et al.
Early strength development of Portland cement mortars containing air classified fly ashes
Cem Concr Res
(1995)
E. Peris-Mora et al.
Influence of different sized fractions of a fly ash on workability or mortars
Cem Concr Res
(1993)
V.M. Malhotra (Ed.), Fly ash, silica fume, slag and other mineral by-products in concrete, Proc. First Intl. Conf.,...

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PapersFluid catalytic cracking catalyst residue (FC3R): An excellent mineral by-product for improving early-strength development of cement mixtures

Abstract

Introduction

Section snippets

Methods

General characteristics of FC3R

Conclusions

Acknowledgements

Waste Management & Research

Thermochimica Acta

Cem Concr Res

Cem Concr Res

Papers
Fluid catalytic cracking catalyst residue (FC3R): An excellent mineral by-product for improving early-strength development of cement mixtures