Chemical Engineering and Processing 46 (2007) 774–780
Reactive distillation: The front-runner of industrial process intensiﬁcation A full review of commercial applications, research, scale-up, design and operation G. Jan Harmsen a,b
Shell Global Solutions, Shell Research and Technology Center Amsterdam, P.O. Box 38000, 1030 BN Amsterdam, The Netherlands b RijksUniversiteit Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands Received 19 June 2007; accepted 20 June 2007 Available online 23 June 2007
Abstract Most industrial scale reactive distillations (presently more than 150), operated worldwide today at capacities of 100–3000 ktonnes/y, and are reported in this paper. Most of these plants started up less than 15 years ago. The drivers, processes, systems, scale-up methods and partner collaborations for this rapid invasion of a new process intensiﬁed technique are explained in this paper. The business drivers are (a) economical (prosperity): variable cost, capital expenditure and energy requirement reduction. In all cases these are reduced by 20% or more, when compared to the classic set-up of a reactor followed by distillation. (b) Environmental (planet): lower emissions to the environment. In all cases carbon dioxide and diffusive emissions are reduced and (c) social (people): improvements on safely, health and society impact are obtained by lower reactive content, lower run away sensitivity and lower space occupation. These industrial reactive distillation systems comprise homogeneous and heterogeneous catalysed, irreversible and reversible reactions, covering large ranges of reactions, notably hydrogenations, hydrodesulfurisation, esteriﬁcations and etheriﬁcation. Various commercial methods for packing heterogeneous catalyst in columns are now available. The systems comprise amongst others: multiple catalyst systems, gas and liquid internal recycle trafﬁc over these catalyst systems, separation, mass ﬂow, and enthalpy exchange. These are integrated optimally in a single vessel, a characteristic feature of process intensiﬁcation. The scale-up methods applied from pilot plants to commercial scale are brute force and modelling. Technology providers CDTECH and Sulzer Chemtech have used these scale-up methods successfully. Barriers perceived and real have also been removed by these companies. Chemical manufacturing companies have also developed their own speciﬁc reactive distillations by their own research and development. These companies, both on their own and in consortia, also developed heuristic process synthesis rules and expert software to identify the attractiveness and technical feasibility of reactive distillation. Heuristic rules and expert software will be presented and supported by examples. Academic research also produced design methods to identify the feasibility of reactive distillation, to determine the feed locations, to select packing types, to sequence columns optimally and also produced methods to design, optimise and control the columns with steady state and dynamic simulation models. The rapid commercial scale implementation of reactive distillation by co-operation of partners in research, scale-up, design and reliable operation can also be seen as a model for rapid implementation of other process intensiﬁcation techniques in the chemical industry. © 2007 Elsevier B.V. All rights reserved. Keywords: Reactive distillation; Industrial; Process intensiﬁcation; Multi-functional; Applications; Research; Scale-up; Design; Operation; Innovation; Stakeholders; Catalytic; Sustainable development; Triple P; Environment; Society; Economic
1. Introduction Reactive distillation, also called catalytic distillation, can be considered as reaction and distillation combined into one new unit operation. Distillation itself is here considered in the wide sense, i.e. the separation by use of vapour–liquid composition
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