Catalysis and Sustainable Green Chemistry PDF
Catalysis and Sustainable Green Chemistry PDF
Catalysis and Sustainable Green Chemistry PDF
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Abstract
Catalysis is a key technology to achieve the objectives of sustainable (green) chemistry. After introducing the concepts
of sustainable (green) chemistry and a brief assessment of new sustainable chemical technologies, the relationship between
catalysis and sustainable (green) chemistry is discussed and illustrated via an analysis of some selected and relevant examples.
Emphasis is also given to the concept of catalytic technologies for scaling-down chemical processes, in order to develop
sustainable production processes which reduce the impact on the environment to an acceptable level that allows self-depuration
processes of the living environment.
© 2002 Elsevier Science B.V. All rights reserved.
Keywords: Catalysis; Sustainable chemistry; Green chemistry; Catalytic processes; Environment protection
0920-5861/02/$ – see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 5 8 6 1 ( 0 2 ) 0 0 3 7 4 - 7
288 G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297
“green chemistry” opposite to a dirty chemistry, but the key aspects of the processes in terms of eco-
simply that each chemical process has a risk asso- compatibility.
ciated with production. The role of chemists and Protection of the environment is not necessarily in
engineers is to minimize this risk and reduce the contrast with economic growth, but certainly the use
impact on the environment to a level sustainable by of new improved chemical technologies is required to
the environment, assuring a good quality of life. If combine these two factors otherwise in contrast. R&D
one looks at the changes that have occurred in the is thus the key for sustainable development. Recent
chemical industry over the last two decades, it can examples, furthermore, indicate that new eco-efficient
be seen that all new processes introduced were moti- processes can give companies the opportunity to gain
vated by a need to reduce the environmental impact or new market positions.
hazardous risks, and achieve better use of resources.
None of the changes were possible however without 1.2. Assessment of sustainable (green) chemical
better process economics, including environmental processes
and social aspects in the cost evaluation. Some ex-
amples of eco-efficient alternative processes to the Another aspect to consider is that often the label
conventional ones are listed in Table 1 together with “green chemistry” is used to indicate technologies for
Table 1
Examples of new eco-efficient catalytic processes
Process Key characteristics
Solutia process
Reduction of N2 O emissions (greenhouse gas)
by reuse as reactant
EniChem process
Reduction of ammonium sulfate waste
Avoids use of toxic hydroxylamine
EniChem process
Reduction of polyalkylate waste
Rhodia process
Avoids use of hazardous catalysts such as
AlCl3 , BF3
Reduced waste formation
Catalytica process
Reduced formation of chlorinated waste
EniChem process
Avoids chlorinated organic by-products (with
respect to the chlorohydrin process)
Aventis process
Reduced waste formation
Reduced corrosion problems
G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297 289
Fig. 1. Overview of the CTSA procedure (see text).
290 G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297
which a careful cost/benefit or assessment study has is popular in the “green chemistry” community, but
not been made. The EPA has defined a procedure for not very precise. It is preferable to use more rigorous
the assessment of cleaner technologies (Cleaner Tech- approaches such as the CTSA procedure mentioned
nologies Substitutes Assessment—CTSA), based on above.
the comparative evaluation of risk, performance, cost, Industrial processes from the beginning have moved
and resource conservation with respect to currently towards more efficient use of resources and improve-
used chemicals/technologies [2]. Key aspects of the ment in selectivity, because both aspects correspond to
assessment procedure are shown in Fig. 1. an improvement in the process economics. An exam-
A more complete analysis should also include life ple of this process is the synthesis of maleic anhydride
cycle assessment, a complex and more costly proce- [7,8]. The catalytic process starting from benzene was
dure. The central aspect of these procedures remains substituted with that using butane about 15–20 years
the quantitative assessment of costs and social and en- ago for the following reasons:
vironmental benefits. Considerable effort is also being
• The loss of two carbon atoms (as starting from ben-
directed to evaluating the relationship between the en-
zene) is avoided.
vironment and health [3].
• The only by-products are carbon oxides and a mi-
“Sustainable (green) chemistry” is thus the natu-
nor amount of acetic acid. With benzene the selec-
ral trend of chemistry, but not an independent fac-
tivity is higher, but several by-products are formed
tor from economic growth, quality of human life and
requiring expensive separation.
health care. The evaluation of new “green” chemical
• The toxicity aspects related to the use of benzene
processes and products should follow a rigorous as-
is avoided, reducing costs related to safety systems
sessment in terms of eco-efficiency, risk minimization
and benzene handling.
and socio-environmental impact which quantitatively
evaluates the costs and benefits of the new process and The butane process fully implements the principles
alternative solutions. of green chemistry:
Table 2
Comparison of the principles of green chemistry and objectives of industrial catalysis
Principles of “green Objectives of industrial Examples
chemistry” catalysis
(iv) Gas-phase reactions reduce the costs of separa- tion. This is not an exception, but rather a common
tion. feature of most of the new chemical processes devel-
(v) The formation of by-products and waste, besides oped over the last two decades.
a loss in selectivity, also implies higher costs of The process to obtain maleic anhydride from bu-
separation. tane was possible only after the discovery of vanadyl
pyrophosphate catalysts which possess unique char-
The butane process has now being adopted world- acteristics of activity and selectivity [8] unmatched in
wide due to the better economics; in this case the all other types of mixed oxides that have been studied
change also is in the direction of environment protec- for this reaction. Catalyst innovation indeed is a key
292 G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297
step in the development of new eco-efficient but also vironment at a sustainable level. The concept of on-site
cost effective processes. production is already used in some new production
processes to avoid the storage of toxic or dangerous
2.2. Downsizing the production of chemicals chemicals (for example, on-site production of HCN) in
the production of toluene diisocyanate. This develop-
The development of sustainable production of ment was made possible by the combined development
chemicals not only requires the development of less of new catalysts and new reactor engineering solutions
polluting and risky production processes, but also which allowed an economic production even in a small
requires a more general change in the approach to size plant. Therefore, innovation in catalyst and cat-
production of chemicals in terms of the global im- alytic reactor engineering was the key element towards
pact on the environment. During the development of minimization of risks and environmental impact.
the petrochemical industry in the middle of the last Another interesting example is the use of H2 O2 as
century the keywords were process integration and a clean reactant. Hydrogen peroxide in combination
upsizing plants in order to reduce the cost of produc- with catalysts such as TS-1 (Ti-silicalite) or related
tion. Typically the cost of production (not considering materials can give rise to a range of highly interest-
environmental costs) increases by a factor of less than ing reactions, some of them listed in Tables 1 and 2.
one with respect to production. The concentration of They include the ammoximation of cyclohexanone,
various chemical processes in one large petrochemical the epoxidation of propene and other small alkenes,
centre reduces the costs of utilities and services, trans- the hydroxylation of aromatics and of linear alkanes,
port, etc. However, these large petrochemical centres plus other reactions of less industrial importance.
have a massive impact on the environment and health, With respect to present commercial processes the new
even when each single process has been improved to processes considerably limit the formation of waste,
reduce its impact on the environment. It is thus neces- and the use of hazardous chemicals (for example,
sary to change the philosophy and go in the direction alkyl hydroperoxide) and reduce process complexity.
of downsizing and decentralizing the production of However, the key parameter for industrial develop-
chemicals to a level acceptable for the environment. ment is the cost of H2 O2 . H2 O2 is produced by only
A change in vision for the production of chemi- a few companies, and very large investments are re-
cals is required. For example, steam cracking is the quired, because H2 O2 synthesis (alkylanthraquinone
main source of olefins for petrochemical and polymer route) is economic only when large quantities are
use, but large plants are necessary and different olefins produced. The cost of H2 O2 today is higher than
form. As a consequence, typically various processes allowable for the commercialization of the above
using these olefins are located near the steam cracking listed reactions, even taking into account the envi-
process. Producing olefins by alkane dehydrogenation ronmental advantages. The introduction of these new
(or oxidative dehydrogenation) may instead allow a processes requires the development of new processes
single type of olefin to be produced in a dedicated plant for the synthesis of H2 O2 , which should meet two
which can be integrated with a downstream petro- requirements: lowering the cost of production and be
chemical process. By designing new catalytic solu- applicable to small to medium size plants.
tions (for example, catalytic membranes) it may even The new H2 O2 synthesis can be vertically inte-
be possible to develop new economic alkane dehydro- grated with a line of production of propene oxide
genation processes on a small to medium scale. There- (PO) from propene (perhaps produced from propane
fore, instead of horizontal integration as in the past, as indicated above) and downstream to a line of PO
vertical integration may be possible in which, for ex- used in the production of polyurethane foams or
ample, starting from an alkane a polymer or chemical polyester resins. Such integration requires medium
may be produced directly in a single integrated line, to small plants (<100–200 kt PO per year) for which
and in the amount needed for local use. This avoids the chlorohydrin process is currently the only viable
costs and risks of transport and storage of chemicals option from the economic point of view (epoxida-
and in addition decentralizing the production of chemi- tion using alkyl hydroperoxides is economic only for
cals may make it possible to maintain the impact on en- large scale processes (>250 kt PO per year)). The
G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297 293
chlorohydrin process, however, forms large quantities 2.3. Towards a catalytic sustainable
of waste water (40 t waste water/t PO) containing (green) chemistry
inorganic salts (ca. 1 t CaCl2 /t PO produced) and sig-
nificant amounts of chlorinated organic by-products Although the environmental budget is rapidly
(formed in ca. 10% yield based on the propene con- becoming larger than the R&D budget in several
sumption). The new route of synthesis of PO by epox- chemical companies, the R&D industrial objectives
idation of propene with H2 O2 on a TS-1 catalyst is have been progressively moved from the medium to
thus preferable to reduce this relevant environmental the short term, without corresponding compensation
impact, but requires the production of H2 O2 on-site by public investments on long-term research. Pro-
(to avoid risks related to its storage and transport), at cess innovation, especially when it involves complete
a low cost and with a level of production compatible process redesign, is a long-term investment. The in-
with its complete use on-site. dustrial research effort on “green chemistry” has thus
A possible route meeting these requirements is been mainly focused on finding short-term solutions,
based on the synthesis of H2 O2 from H2 + O2 mix- like substitution of hazardous chemicals, solvents,
tures using Pd-based catalysts. There are, however, etc. which can revamp plants, more than on devel-
a series of problems related to reactor design (espe- oping completely new solutions which require much
cially to assure safe operation), the H2 O2 productivity higher investments. In addition, the largest part of the
and concentration which can be obtained, and cata- environmental budget is related to cleanup technolo-
lyst optimization to maximize selectivity towards H2 . gies to make sure that all emissions meet legislative
The solution of these problems, which requires an in- regulations.
tegrated reactor and catalyst approach, is the critical It is thus possible to identify two main directions
step to enable the new concept of on-site eco-efficient in catalysis research related to sustainable (green)
PO synthesis discussed above. Catalytic membranes chemistry:
are a solution under investigation to eliminate the
• A long-term approach (breakthrough approach),
problems indicated above.
based on innovation in catalytic materials chem-
This example evidences the complexity of prob-
istry and use of unconventional reaction conditions
lems encountered in developing processes of sustain-
which will provide the driving force for devel-
able chemistry. Scaling-down chemical processes is a
oping new solutions (catalysts, technologies and
future requirement to develop sustainable production
processes). Renewed effort is also necessary in
processes which reduce the impact on the environment
multidisciplinary approaches and in technologies
to a level acceptable for autopurification processes. It
which allow making reactions under mild con-
must be noted, however, that the eco-indexes to eval-
ditions (electro- and photo-catalysis, reactions in
uate this acceptable level of eco-compatibility must
plasma and with dielectric barrier discharges, etc.).
be related to environment parameters (for example,
• A short–medium-term approach (evolutionary ap-
maintain the eco-diversity of species) and not only to
proach), mainly focused on the improvement of cur-
chemical parameters (like the presence of pollutants,
rent catalytic technologies and processes.
metal ions, etc.), differently from the common ap-
proach. Legislative limits, which are the driving force The largest part of industrial effort is focused on
for innovation towards R&D for sustainable chemistry, the second direction. Combinatorial catalysis is often
must also be related to these eco-indexes. A step for- classified in the first area, being aimed at discovering
ward with respect to the current situation where limits new catalytic materials by a fast screening procedure.
are applied mainly on the basis of the “precaution” However, breakthrough catalytic technologies and pro-
concept is thus necessary. cesses may derive only from the identification of prob-
Catalysis plays a central role in this process of lems and the testing of unconventional ideas, due to
scaling-down, because new solutions are required in the complexity of the catalytic and sustainable chem-
terms of both process miniaturization and use of more istry problems. Fast, but automatic, catalyst screening
sophisticated technologies (for example, catalytic procedures assume a linearity of effects which is not
membranes). effectively true.
294 G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297
2.4. Catalysis, green chemistry and organic syntheses of substituted phenols of large interest as interme-
diates in the production of fine chemicals. How-
The discussion in the previous sections has shown ever, phenol is more reactive than benzene towards
that the concept of “green chemistry” may be ap- hydroxylation and therefore the problem is how to
plied with severe limitations in the production of base stop reactivity to maximize selectivity. One solution
chemicals, because even though the concepts are al- is to use biphasic systems, where the products due
ready well established, the next generation processes to the partition coefficient are rapidly taken away
involve different problems from those suggested by from the catalyst. By using biphasic FeSO4 with a
“green chemistry” principles. Indeed, the latter were pyrazine carboxylic acid ligand and trifluoroacetic
especially designed with reference to the synthesis acid as cocatalyst in a benzene–water–acetonitrile
of organic chemicals, for which there is an effective biphasic system it is possible to achieve 97% selec-
need also in today’s commercial production to pass tivity to phenol at about 8% conversion (Fig. 2b)
from stoichiometric reactions to catalytic ones, to use [13]. Due to the nature of the chemical used, it
cleaner solvents, to reduce waste, and to maximize is difficult to consider the applicability of this
atom efficiency [9,10]. A “green chemistry” expert process and solution to large scale products (like
system to help in surveying the field and choosing phenol), but it may be an interesting solution for
the preferable solvent, reaction conditions and syn- the synthesis of substituted phenols.
thetic methodologies is also available online (http:// • Ionic liquids represent a new class of highly inter-
www.epa.gov/greenchemistry/tools.htm). esting and versatile solvents. Based around imida-
Catalysis is also in this case a fundamental com- zolium salts, these solvents are liquid over a wide
ponent of the innovation towards cleaner production range of conditions, but have a minimal vapour
processes. A few examples are given below to high- pressure. They also possess interesting properties
light new possibilities for catalysis in eco-compatible which are a combination of the characteristics of
organic syntheses. In most of the cases however pro- water and organic solvents. They can be used as
cess economics and catalyst stability have not been non-usual solvents which allow interesting reac-
demonstrated: tions. For example, enzyme Candida Antartica
catalyzes the oxidation of octanoic acid by H2 O2
• Noble and non-noble metals are widely used in se- to form a peroxo acid which then is able to oxidize
lective hydrogenation of organic molecules, but se- alkenes with good yields (Fig. 2c) [14].
lectivity is not complete. Charged transition metal New catalytic organic synthesis methodologies thus
complexes (ferrocenyl-rhodium, for example) may offer several possibilities for a relevant improvement
be immobilized on alumina or silica by functional- in the eco-compatibly of fine chemicals production,
izing the latter by grafting a heteropolyanion which allowing a drastic decrease in the E factor. It should
then anchors the charged transition metal complex. be noted, however, that there is a factor of around
This catalyst allows quantitative hydrogenation re- 100 between the waste produced in the production
actions (Fig. 2a) [11] and good turnover numbers. of fine chemicals and base chemicals, for example,
This example shows the possibility offered by an- but a factor much higher between the volume of base
choring or tethering metal complexes to solids. A chemicals produced (as well as refinery products) and
series of interesting behaviours has also been found fine chemicals. Therefore, in terms of global impact
by tethering metal complexes to the walls of meso- it is the production of refinery and base chemicals
porous materials (like MCM-41). Encapsulated which should be primarily addressed, but this requires
metal complexes (often defined ship-in-a-bottle a longer term approach.
samples) may also be included in the same general
class of complexes in constrained environments 2.5. The use of alternative reaction media
[12].
• The hydroxylation of benzene to phenol is an inter- The use of alternative reaction media is a concept
esting industrial reaction (see Tables 1 and 2), but particularly emphasized in green chemistry, because
also a model reaction for the synthesis of a variety the problem is seen from the organic chemistry
G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297 295
perspective (as discussed above) and thus there is a characterized by high diffusivity, low viscosity, and
need to substitute toxic solvents with non-toxic sol- intermediate density. This may give rise to consid-
vents, as well as to decrease the amount of waste erable improvements in chemical reactions, since all
(mainly related to the large volumes of solvents for phenomena which are related to mass-transfer phe-
the reactions). Emphasis is thus given to novel solvent nomena and which can limit the rate of reaction may
systems (for example, ionic liquids and biphasic sys- be overcome by exploiting these properties. Health
tems), non-solvent reactions and supercritical solvents and safety benefits include the fact that most SCFs,
(CO2 , in particular). scCO2 and scH2 O, are non-toxic, non-carcinogenic,
Supercritical fluid technology has been around for and non-flammable, a clear advantage with respect to
many years, but has found commercial application conventional organic solvents.
mainly for extraction processes. The recent progress in Specific further advantages might be exploited for
engineering and equipment technology for operations catalytic applications in the field of petrochemical and
under pressure (which parallel a reduction in cost) has fine chemicals synthesis:
made affordable the use of supercritical fluids of new
reaction media. • The extraction properties of SCFs may be exploited
Supercritical fluids, SCFs, are gases compressed to separate products from by-products, or to recover
until their density approaches that of liquids. Such homogeneous catalysts, replacing conventional or-
compression can occur only above the “critical ganic solvents and improving performances with
temperature” of the fluid, since at lower temperatures respect to the latter. An application of this might be
the fluid liquefies on compression. Therefore, an SCF the in situ regeneration of heterogeneous catalysts
is a gas which displays some of the properties of a which deactivate due to the formation of heavy
liquid. The advantages of using supercritical fluids residues.
are related to the absence of toxic residues, relatively • Easy separation of the SC solvent from the prod-
low temperature needed for the extraction process, ucts allows obtaining pure products without solvent
and higher solvent power of SCFs. residues.
SCFs also offer interesting opportunities for • The rate of reaction may be considerably in-
chemical syntheses with solid catalysts. SCFs are creased with respect to reactions carried out with
296 G. Centi, S. Perathoner / Catalysis Today 77 (2003) 287–297
Table 3
Examples of catalytic reactions in supercritical fluidsa
Type of Reaction Catalyst Reaction conditions Effectb
reaction
Alkylation Isobutane + H–Y (dealuminated) Solvent: isobutane, Increase activity, increase lifetime
isobutene T = 50–140 ◦ C,
P = 3–5 MPa
Esterification Oleicacid + Ion-exchange resins Solvent: CO2 , Increase activity
methanol T = 40–60 ◦ C,
P = 0.9–1.3 MPa
Hydrogenation Fats and oil Supported Pd Solvent: propane, Increase activity, increase selectivity
T = 50–100 ◦ C,
P = 7–12 MPa
Isomerization 1-Hexene Supported Pt Solvent: CO2 Increase activity, selectivity and lifetime
(cosolvent: pentane),
T = 250 ◦ C,
P = 18 MPa
Oxidation Toluene to Co/alumina Solvent: CO2 , Increase selectivity
benzaldehyde T = 100–200 ◦ C,
P = 8 MPa
a Elaborated from [15].
b Effect of using supercritical conditions with respect to subcritical conditions.
conventional solvents. This is may be due to several neous catalytic reactions, and at the same time provide
different effects: new paths for sustainable chemistry.
◦ Higher diffusivity in the SC solvent of reac-
tants; in heterogeneously catalyzed reactions,
often inter-particle mass-transfer may be the 3. Conclusions
rate-limiting step for very rapid reactions. With
SC solvents, this problem is overcome due to Catalysis is a key technology to achieve the objec-
the fact that the boundary layer is considerably tives of sustainable (green) chemistry, but an innova-
reduced in thickness. tive effort is necessary in the design of new catalysts
◦ High miscibility of the SCF with other gaseous and catalytic technologies (including reactor engineer-
reactants. ing) and also in reconsidering all chemical produc-
◦ Presence of a single homogeneous phase instead tion processes with the objective of developing small
of a gas–liquid biphasic system again may be and delocalized plants for on-site production. This
helpful to overcome the problems associated long-term objective requires an even more innovative
with mass-transfer. effort in the direction of using catalysis in unconven-
◦ The SCF may take directly part in the reaction, tional conditions.
and all the above mentioned advantages may
contribute in enhancing the rate of reaction.
• The selectivity of the process may be affected as References
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