CHEMICAL ENGINEERING TRANSACTIONS
VOL. 26, 2012
A publication of
The Italian Association
of Chemical Engineering
Online at: www.aidic.it/cet
Guest Editors: Valerio Cozzani, Eddy De Rademaeker
Copyright © 2012, AIDIC Servizi S.r.l.,
ISBN 978-88-95608-17-4; ISSN 1974-9791
Preserving Safety and Improving Yield Performances in
Methanol Processes
Zohreh Ravaghi-Ardebili
a
, Flavio Manenti*
a
, Nadson M. Nascimento Lima
b
,
Lamia Zuniga Linan
b
, Silvia Cieri
c
, Marco Restelli
c
, Giulia Bozzano
a
a
Politecnico di Milano, CMIC dept. “Giulio Natta”, Piazza Leonardo da Vinci 32, 20133 Milano, ITALY
b
University of Campinas (UNICAMP), Department of Chemical Processes, PO Box 6066, 13081-970, Campinas,
São Paulo, BRAZIL
c
Novartis Vaccines & Diagnostics, Via Fiorentina 1, 53100 Siena, ITALY
flavio.manenti@polimi.it
The industrial best practice for methanol synthesis is the use a fixed-bed tubular reactor. The
exothermic nature of methanol synthesis, the possibility to activate the methanation reaction (intensely
exothermic) and the discrete nature of temperature acquisition throughout the reactor claim for novel
technological solutions for process control and optimization. Specifically, the aim of this work is to
monitor the hot-spot temperature and to manipulate it to improve the yield of methanol.
1. Introduction
Even though many improvements have been made since its first industrial technology, in 1923, and a
series of new production technologies are being developed (Lange, 2001; Olah et al., 2009; Basri et
al., 2009; Gomez-Castro et al., 2010; Mayra and Leiviska, 2009; Sie et al., 2009), methanol is still
largely produced, with very low conversions, from natural gas, specially via synthesis gas (or syngas,
CO and H2 mixture). The latter is produced by means of steam reforming operations. Moreover, the
methanol process is usually characterized by high potentiality, relatively high pressure, and some side
reactions that must be controlled to prevent any operational risk.
In this context, it is difficult to maintain the performances of methanol conversion, while the safety of
the operations must be fulfilled; this further contributes to the yield in methanol less than 7 %. For
example, the well-established directives are to operate the methanol synthesis reactor in the range
500-540 K (Lommerts et al., 2000; Graaf et al., 1986; Graaf et al., 1988). Lower temperatures
correspond to poor catalyst activity, whereas higher temperatures activate the so-called methanation
reaction:
2 4 2
3 CO H CH HO (1)
Even if the methanation reaction, which is provided by the copper coating, takes place at more than
570 K, the safety threshold of operation is estimated around 540 K. It accounts for the fact that the
overall reaction process from syngas to methanol is exothermic and, therefore, the reaction
environment moves towards higher temperatures. In addition, being the system kinetically controlled
for the first part of the reactor and thermodynamically controlled for the remaining part, the temperature
profile of the methanol reactor is characterized by a maximum so called hot-spot (Manenti et al.,
2011a; Manenti et al., 2011b). Nevertheless, the temperature is measured by a multi-thermocouple,
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