Professional Documents
Culture Documents
Anton A. Kiss,*
,,
Alexandre C. Dimian,*
,,
and Gadi Rothenberg*
,,
Van t Hoff Institute for Molecular Sciences, UniVersity of Amsterdam, Nieuwe Achtergracht 166,
1018 WV Amsterdam, The Netherlands, Akzo Nobel Chemicals B.V., Velperweg 76, Arnhem, The
Netherlands, and Yellow Diesel B.V., Roetersstraat 35, Amsterdam, The Netherlands
ReceiVed May 24, 2007. ReVised Manuscript ReceiVed September 27, 2007
The properties and use of biodiesel as a renewable fuel as well as the problems associated with its current
production processes are outlined. A novel sustainable esterication process based on catalytic reactive distillation
is proposed. The pros and cons of manufacturing biodiesel via fatty acid esterication using metal oxide solid acid
catalysts are investigated. Finding catalysts that are active, selective, and stable under the process conditions is the
main challenge for a successful design. The best candidates are metal oxides such as niobic acid, sulfated zirconia,
sulfated titania, and sulfated tin oxide. Rigorous process simulations show that combining metal oxide catalysts
with reactive distillation technology is a feasible and advantageous solution for biodiesel production.
1. Introduction
Sustainable energy management is a major concern of the
modern society. The increasing energy demand makes the imple-
mentation of sustainable fuels a crucial issue worldwide.
1,2
Biodie-
sel has become increasingly attractive because it is made from
renewable sources and combines high performance with environ-
mental benets.
36
The idea of using vegetable oil as fuel for diesel
engines is over a century old. In fact, Rudolph Diesel himself
demonstrated the performances of his engine using peanut oil as
fuel. Unlike petroleum diesel that contains hydrocarbons, biodiesel
consists of a mixture of monoalkyl esters of long-chain fatty acids.
These are typically produced by (trans)esterication.
7
Biodiesel has several advantages over petroleumdiesel: it is safe,
renewable, nontoxic, and biodegradable; it contains no sulfur and
is a better lubricant.
4,8
Despite the chemical differences, these two
fuels have similar properties and performance parameters (Table
1).
912
Along with its technical advantages over petroleum diesel,
biodiesel brings several additional benets to the society: rural
revitalization, creation of new jobs, and less global warming.
An important characteristic of diesel fuels is the ability to
autoignite, quantied by the cetane number (cetane index).
Biodiesel not only has a higher cetane number than petroleum
diesel but also has a higher ash point, meaning better and safer
performance. Blends of biodiesel and petroleum diesel are
designated by a B followed by the vol % of biodiesel. B5
and B20, the most common blends, can be used in unmodied
diesel engines.
5
Remarkably, biodiesel is the only alternative
fuel currently available with an overall positive life-cycle energy
balance (Figure 1), producing 3.2 units of fuel product energy
per unit of fossil energy consumed, compared to barely 0.83
units for petroleum diesel.
3
The presence of oxygen in biodiesel (10%) improves
combustion and reduces CO, soot, and hydrocarbon emissions
while slightly increasing the NO
x
emissions. Figure 2 shows
the biodiesel versus petroleum diesel emissions as well as the
amount of CO
2
per distance produced by various fuels.
4,11
One
comprehensive study showed that using B20 in trucks and buses
would completely eliminate the black smoke released during
acceleration.
4
There are ve primary ways for making biodiesel: (i) direct
use and blending of vegetable oil,
7
(ii) use of microemulsions
* E-mail: tony.kiss@akzonobel-chemicals.com (A.A.K.); alexd@
science.uva.nl (A.C.D.); gadi@science.uva.nl (G.R.). Fax: +31 20 525 5604.
University of Amsterdam.