Sostenibilidad Industria

9.
Chemical industry
and sustainable development
9.6.1 Sustainability inextricably linked to the concept of development

which, combined, form the well-known expression
The problem of sustainability has been an issue of sustainable development.
worldwide importance for over 15 years and has been The utilization of scientific knowledge for
the object of two extremely important summit practical purposes through the use of technology has
meetings (Earth Summit, Rio de Janeiro, 1992; World grown enormously during the various industrial
Summit on Sustainable Development, Johannesburg, revolutions from the Eighteenth century onwards, and
2002). It rose to the attention of world public opinion has led to a real explosion of technological
in 1987 with the presentation of the report Our development in our present times. Alongside the
common future (WCED, 1987) by the World obvious benefits, a whole series of problems arose as a
Commission on Environment and Development. It is result of the uncontrolled exploitation of the Earth’s
in this report that the most commonly cited definition resources and the effects produced on the climate,
of sustainability (often associated with the name of the environment and mankind. This led to an increasing
Norwegian Prime minister, Gro Harlem Brundtland, sensitivity, which has developed in the last few
who chaired the Commission) can be found: decades, towards the question of protecting
“sustainability is the ability to meet the needs of the environmental resources. It has become evident that
present, without compromising the ability of future the environment is a critical resource that is rare and
generations to meet their own needs”. precious; it must be protected, defended, handled
The aspects which are most directly involved in and preserved with care.
problems of sustainability relate to population growth, Not only the problems, but also the solution to the
food availability for nourishment, energy problems, problems associated with development should derive
the destruction of natural resources, global climate from scientific knowledge and its application in newly
change, utilization of water sources, the generation available technologies.
and dissemination of toxic substances and waste
products. These represent genuine challenges. The industrial system and sustainable development
To overcome the challenge of sustainability, the
Sustainable development and technological new technologies developed as a result of innovation
progress must form part of a new model of industrial progress
Even if sustainability without development may which is capable of combining economic growth with
seem to be a relatively simple solution at first sight, in social and environmental responsibility. In reality,
reality, this option cannot be proposed; when there is a growing awareness today that many of the
examined more carefully, it cannot lead to the level of concerns of a non-financial nature linked to the
sustainability which should be guaranteed. For problem of sustainability have a direct impact on the
example, it is difficult not to take into consideration long term value for shareholders. An increasing
the above-mentioned correlation between a sustainable number of large international companies feels the need
growth of the world population and an improvement in to focus their activities and base their final statements
the quality of life in developing countries. The concept not only on economic profit, but also on the
of sustainability therefore cannot but prove to be production (or less destruction) of an environmental
VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 879

SUSTAINABILITY
and social value. This approach is commonly known as done within an extremely wide perspective, beyond the
TBL (Triple Bottom Line): the three lines (which single process considered and even beyond the single
represent society, economy and environment) are in company, just as an economic analysis must overcome
continuous movement as a result of economic, social, classical cost and performance concepts to include
and environmental cycles and contrasts; they move environmental and socio-economic protection (Bakshi
independently of each other creating areas of friction and Fiksel, 2004). A holistic vision of the whole
from which conflicts emerge (Elkington, 1997). system is essential for understanding and modelling
A significant example of this new awareness is the complex interactions between industry, society and
represented by the World Business Council for ecosystem. It involves the intervention of various
Sustainable Development (WBCSD), founded in 1990, disciplines, from technical reference disciplines such
which brings together over 150 foremost worldwide as engineering, chemistry and biology, to medicine,
companies, belonging to 34 countries and present in economy, law, ethics and social sciences. Creating a
more than 20 industrial fields. In a series of studies and sustainable industrial system must relate to the whole
leaflets published during its activities, the WBCSD life cycle of the product or process; it must produce
intends to act as a catalyst towards sustainable things eco-efficienly by reducing the environmental
development and demonstrate that the business world, impact of the production activity to the minimum; a
as a primary user of natural resources and new cyclic model, which is closer to the flows of natural
technologies, has much to gain from protecting the ecosystems in which waste products have a value as
global ecosystem (Schmidheiny, 1992). Sustainability- bionutrients, must be favoured instead of a linear
oriented actions can directly contribute towards both industrial system.
the tangible financial value of enterprises by favouring All of this must naturally take place in small steps;
growth, lowering costs and reducing risks, and also the approach to industrial sustainability is in its early
towards improving the intangible assets, such as image, infancy and still a long way from an overall change in
strategic relations, human capital and innovation. attitude to the commonly accepted way of ‘doing
The system of Dow Jones Sustainability World business’ which has been defined as downright
Indexes, created in 1999, which comprises over 300 ‘creative destruction’. Currently, the most common
companies of 60 industrial groups in 34 different approach to sustainable development is limited to the
countries, with a market capitalization (February setting up of single processes evaluated from a
2004) of approximately 6,500 billion dollars, technological standpoint as more eco-compatible and
represents the first example of global monitoring of therefore capable of obtaining greater consent. This is
the performances of the main world companies which a relatively restricted approach, extremely distant from
operate paying careful attention to sustainability the planetary and multigenerational vision inherent
issues. The aspects of sustainability are evaluated in the definition of sustainability mentioned at the
according to a series of criteria which vary from beginning, and also from the use of assessment
generating long-term profit to management culture techniques such as a detailed life cycle analysis, but it
and company organization; from renewing production is important, however, for starting the whole process.
processes and products to the image and reputation
that the company has acquired. More generally, what is Measuring sustainability
assessed is the company’s ability to create value for the It can be seen, from what is described above, that
whole of its stakeholders, interest bearers, intended in sustainability can be considered as three-dimensional:
a general sense and progressively in the widest sense: ecological, economic and social. Sustainable
shareholders, employees, clients, as far as the local development is therefore an optimization of these
and worldwide community. A leading company in the three dimensions. To put theory into practice, it is
field of sustainability must have a strategy which is necessary to have instruments that quantify the
capable of integrating an effective ability to compete reduction in the environmental impact, as well as the
and create profit with social, environmental and economic and social benefit generated by the
economic aspects over a long period of time. It must transition to a new product, process or system.
create innovative products and services, focused on The social aspect of sustainability is the most
technologies and systems which utilize natural, social difficult to quantify, and this issue is the least defined.
and financial sources effectively and efficiently. It The quantification of economic and environmental
must pursue a policy of transparent communication aspects has, on the contrary, been the object of
towards shareholders and the public, as well as loyalty considerable activities and is generally known as
in relations with the clients. eco-efficiency analysis. During its activity, the
As sustainability is a property of the system in its WBCSD has publicized the concept of
entirety, re-planning the industrial system must be eco-efficiency (WBCSD, 2000) embodied in the 3 R
880 ENCYCLOPAEDIA OF HYDROCARBONS

CHEMICAL INDUSTRY AND SUSTAINABLE DEVELOPMENT
principle: Reduce, Reuse, Recycle, which aims to associated with potential responsibility and internal or
integrate the environmental aspect with the economic external intangible costs. For a correct TCA analysis,
aspect in the economically practical production of standardized methods developed and implemented in
goods and services with a reduced ecological impact software are currently available.
(creating more value with less impact). The objective
of eco-efficiency is consequently to maximize the
value, at the same time minimizing the negative 9.6.2 Sustainability in the chemical
impact on the environment. An eco-efficiency index is industry
therefore defined, which takes into consideration the
economic and ecological aspects: The chemical industry has an extremely important role
in the global industrial sector. On a world scale, it
product or service value
eco-efficiency index 1121111111244 produces an annual turnover of over 1,700 billion euro,
environmental impact
generating 9% of international commerce and offering
The eco-efficiency can be quantified through an work to over 10 million people. In the value generation
analysis of seven key indicators: a) reduction in the chain, the chemical industry is positioned upstream of
use of raw materials; b) reduction in the use of energy; numerous sectors such as the building, transport, food,
c) reduction in the dispersion of toxic substances; health, personal and household hygiene, clothes,
d ) improved recyclability; e) maximization of the electronics, etc., providing intermediates for
sustainable use of resources; f ) prolonged duration; downstream industries and also directly contributing to
g) growth in service performances. As already creating materials for the consumer market. Indeed,
mentioned, the eco-efficiency index does not take into today’s society would not exist without the chemical
account all three pillars of sustainable development as industry.
it is based on economic and environmental efficiency, As a result of its extremely strategic nature
and does not consider the social aspects. It is, connected to numerous sectors essential for
nevertheless, a key indicator for orienting decisions of modern-day society, and as a manufacturing industry
the financial and political world. which substantially transforms raw materials into
The most well-known instruments for quantifying products, the chemical industry is fully involved in the
eco-efficiency are Life Cycle Assessment (LCA) problems relating to industrial sustainability outlined
relating to the quantification of environmental above (Jenk et al., 2004). It is often considered by
impacts, and Total Cost Assessment (TCA) for value public opinion as being mainly responsible for
quantification. In life cycle assessments, all aspects problems relating to environmental degradation, and
concerning environmental impact are quantitatively the negative consequences of production, distribution
taken into consideration by means of a ‘from cradle to and the use of chemical products have now become of
grave’ analysis. This approach takes into account the increasing social concern.
whole life cycle of a product or system (and all parts Because it is situated upstream of numerous sectors
of the relative production process), from raw materials producing both industrial intermediates and
to final disposal, including distribution, use, reuse and end-products for consumers, the chemical industry has
recycling. Energy, materials and water are used in all quite a varied structure. It comprises fields ranging
these phases, which can generate waste products. from petrochemicals (on the boundary between
When the product becomes obsolete, it can be chemistry and refining) to bulk chemicals (large
renewed, reproduced or recycled. It should be noted industrial intermediates), inorganic products, organic
that this approach is very different from that adopted intermediates and polymers, through to fine and
ten or twenty years ago, when the sole interest of specialty chemicals, dyes, pharmaceuticals and
manufacturers and legislators was directed at waste agricultural products. This diversified reality obviously
products and production scrap. In reality, the multiplies problems relating to sustainability, but at the
environmental impact of production is not necessarily same time, enhances opportunities for development
the most important one. that can derive from them.
LCA must also be associated with total cost These problems can be summarized as follows:
assessment (TCA), a financial analysis method which pollution caused by chemical processes and products;
integrates conventional financial assessment and risks created by dangerous chemical products;
places a monetary value on environmental impacts exhaustion of sources of raw materials (Mestres,
during the single life cycle phases. In this way, a TCA 2004). Chemical products are released into the
highlights and takes into account a whole series of environment more or less continuously during
costs and savings which are not considered in a production processes as plant leakages, such as
traditional approach, including future contingent costs gaseous emissions, waste products sent for disposal, or

SUSTAINABILITY
waste water. A significant share of end-products of the chemical status quo as far as possible, only limited
chemical industry is dispersed into the environment, improvements can be made, often at enormous and
not only by the chemical industry which created them, highly unproductive costs.
but also by the industries that use them in the various Not by chance has the announced introduction in
applicative fields and by the final consumers. The the European Union of the so-called REACH
difference between the negative effects deriving from (Registration, Evaluation and Authorization of
polluting products and dangerous products should also CHemicals) system been arousing controversy. On the
be pointed out. Highly toxic, flammable, explosive one hand, it is considered by many as being too
products can be the cause of dramatic events, ambitious, complex and onerous, if seen as a further,
involving people and things to a considerable extent, more advanced attempt at regulation; on the other
but always on a local level. Polluting products are hand, too insufficient to contribute to the real leap
certainly harmful and dangerous for the environment; forward in quality that many are awaiting in the
they can exert their effects over long periods of time construction of a sustainable industrial society. The
(effects which cannot be so easily and unequivocally REACH system has been defined (2001) in the White
recognized) and on an global scale. Protection from Book of the European Commission which outlines the
accidents caused by the release of chemical products, new strategy for chemical substances, aiming at a
and preventing the effects of pollution must therefore sustainable development. The essential feature of the
be kept quite distinct. The third problem identified is new system is that industry will have to take on an
linked to the decline or exhaustion of raw materials active role, and sustain the relevant costs, in providing
(even for the local environment), whether they be of a essential information for evaluating the danger of
mineral or fossil organic nature, leading to existing and new products, assuming the responsibility
modifications in price and the economic balance of and burden of the task. In other words, enterprises will
production and commercial activities. This will lead to have to take on the task of carrying out
the development and utilization of new or modified characterization tests (physical, chemical,
processes and products to allow a shift towards the use toxicological, eco-toxicological properties) of the
of renewable sources as raw materials. products, and providing a central data bank and users
The objectives that the chemical industry must downstream (including consumers) with detailed
pursue to solve these problems can therefore be information. The objective is to complete this
summarized as follows: a) reduction in the use and operation within 2012, starting with the most
generation of polluting chemical products in chemical widespread or most dangerous substances (the
processes; b) reduction in the use of dangerous implementation times, however, are still under
chemical products in chemical processes; c) reduction discussion).
in the harmful effects of end-products; d ) reduction in
the use of limited and non-renewable raw materials. Green chemistry
The growing urgency of the inherent problems, A more radical solution to the problems specified
together with the increasing awareness and sensitivity above consists in the use of intrinsically cleaner
in this respect, has led in the last few decades to the processes and intrinsically safer products (Anastas and
introduction of increasingly stringent regulations Williamson, 1998; Tundo et al., 2000). It is known that
aimed at regulating industrial processing procedures the risk can be defined as the product of the hazard of
and the characteristics of the products used and sold, a certain agent, for example a chemical substance,
the quality and quantity of the emissions, as well as times the exposure to the same agent:
effluents and waste products generated (Gaertner
risk hazard exposure
et al., 2003). At the same time, the more responsive
manufacturers (within the sphere of responsible care The regulative approach (command and control)
policies) have responded by voluntarily often adopting imposed by laws and regulations is essentially directed
even more severe measures for the reduction of towards minimizing the exposure factor, for example
emissions, the treatment of waste products and, when by controlling emissions or imposing the use of
possible, the recycling of end-products at their protective measures. The risk can be much more
life-end. The limits of this approach, which can be radically reduced, however, by diminishing or
defined as (self-)regulation, are evident. First of all, it eliminating the other element of the expression, i.e. the
only responds to the first two categories of problems hazard: if an agent is not dangerous, it obviously
outlined above, linked to pollution and safety, without cannot give rise to a significant risk. This innovative
paying any attention whatsoever to the issue of the approach is known by the name of green chemistry.
exhaustion of raw material sources. Furthermore, Green chemistry arose from simple considerations,
based on the assumption of preserving the existing such as the fact that it is better to avoid the formation

of waste products than to treat them and dispose of concept that the assessment parameters of a new
them after they have been produced; and that it is better chemical technology do not stop at the production
to avoid the use of dangerous or potentially polluting yield, and properties and efficacy of the product or a
products and processes than adopt expensive measures particular reagent in the applications for which it has
for reducing the risks and emissions. The green been designed. It must be taken into account that the
chemistry strategy is focused on concepts such as: a) chemical processes we are designing will have an
eliminating the use of raw materials, intermediates and impact on the people who come into contact with the
products which are toxic and dangerous; b) reducing as materials produced and the production processes used,
much as possible the quantity and hazard of emissions and on the environment in which they are present. In
and waste products from production processes, also other words, the evaluation of a process or product
through the reuse of possible by-products; c) reducing cannot but completely fall within the extensive
energy consumption as much as possible; d) sustainability assessment methods described above,
eliminating the use of solvents, especially those which i.e. making use of total Life Cycle Assessment (LCA)
are most harmful for the environment; e) increasing the and Total Cost Assessment (TCA) analysis concepts.
use of renewable raw materials. From this point of view, green chemistry can be
Green chemistry is an essentially innovative inserted within the context of industrial ecology, of
approach, as it proposes to exploit the propensity which it uses instruments and guidelines (Graedel,
towards innovation which has characterized the 1999). The following objectives emerge: a) to adopt an
chemical industry right from the start. Green chemistry assessment perspective for chemical products and
essentially means using chemistry to prevent risks and processes extended to the whole life cycle; b) to take
pollution. In addition to being innovative, the green into account in the assessment the environmental
chemistry approach is also non-regulatory and takes impact of the activities of the suppliers and customers;
into account economic aspects. Using new processes c) in the case of long-lasting products, recyclability
which do not have to incur too many costs associated must also be taken into consideration; d ) in the case of
with increasing safety measures, risk protection, dissipative products (those consumed in the process
emission control and waste disposal (or that do not use of carrying out their purpose), the distribution phases,
raw materials close to exhaustion) constitute excellent circulation and use must be considered along with the
business, if well planned. It should be remembered that production; e) to design both processes and products
economic advantages are considered as being a main with a low environmental impact.
boost for its success. Various specific indicators have been developed
The basic concepts of green chemistry have been within the context of general sustainability
encoded in 12 principles (Anastas and Warner, 1998), measurement techniques and instruments (Curzons
which identify the main guidelines in which the et al., 2001; Constable et al., 2002), illustrated in Table 1.
development and definition of new clean processes These parameters are not directed towards major
and products can be inserted. These include concepts problems of overall sustainability and are not intended
already widely discussed before, starting with the first as tools for identifying great company strategies. They
and fundamental concept which prescribes avoiding have been conceived as auxiliary means in defining
the formation of waste products rather than having to research and development policies, aimed at
treat and dispose of them after they have been developing new processes and improving those already
produced. At the basis of green chemistry is the existing within a short-medium term scenario.
Table 1. Measurement parameters of the sustainability of a chemical process
Indicator Definition
Effective mass yield (%) Product mass 100/mass of non-benign materials used
E-factor Waste-product mass/product mass
Atom economy (%) Molecular weight useful product 100/molecular weights reagents sum
Mass intensity Total mass used in the process/product mass
Carbon efficiency (%) Quantity of carbon in the product 100/total carbon quantity in the reagents
Reaction mass efficiency (%) Product mass 100/reagent mass

SUSTAINABILITY
The effective mass yield measures in percentages subjective. The result is called Environmental
the mass proportion of desired product obtained Quotient (EQ).
compared to the mass of all the non-benign materials Atom Economy (AE), otherwise defined as atom
involved in its synthesis. This indicator is extremely utilization or atom efficiency, is another indicator with
interesting as it emphasizes the hazard of the reagents, an extremely simple and intuitive meaning. It indicates
a consideration which is normally absent in yield the amount of reagents that remains in the desired
evaluation. Benign materials refer to those reagents, product on the basis of the reaction stoichiometry
solvents or by-products which involve no risks for (Trost, 1991). The definition of atom economy is
health or the environment. The definition, however, based on the stoichiometry, deliberately ignoring the
suffers from an evident lack of clarity, especially for yield and excess of one reagent compared to the
limited risk cases; moreover, information relating to others, as well as the presence of catalysts and
risk is not always easily available, often making the solvents. In the context of the atom economy concept,
use of this indicator difficult. a reagent is a substance which is at least partially
The E-factor, on the other hand, has the advantage incorporated in the product (or in a reaction
of simplicity, concentrating on the production of waste intermediate).
products accompanying a certain quantity of the Unlike atom economy, the Mass Intensity (MI) not
desired product (Sheldon, 2000). The theoretical only takes into consideration the stoichiometry but also
E-factor, linked to the stoichiometry of the reaction, the yield, the solvents and auxiliaries used in the
obviously represents the minimum value; the real reaction and purification: in short, the total mass used
value, linked to the actual reaction yield, is normally in the process, except for that of water, and compares it
much higher as the yield acts on both the numerator, with the product mass obtained. The following relation
increasing it, and the denominator, decreasing it. It is exists between the mass intensity and E-factor:
also evident that the evaluation criterion of the
E-factor MI 1
E-factor can vary surprisingly when passing from the
evaluation of a petrochemical process to the synthesis (to the extent in which the solvents and auxiliaries
of a pharmaceutical product, as shown in Table 2: for a considered form a waste product). The mass intensity
petrochemical derivative produced in a quantity in the is sometimes transformed into mass productivity,
order of millions of tonnes, the E-factor is less, in fact expressed in a form homogeneous with the effective
much less than 0.1, whereas it can exceed the value of yield and atom economy:
100 for a pharmaceutical product. This is due to the
mass product mass 100 100
productivity total mass used in the process MI
fact that in the pharmaceutical sector the synthesis 111111331111244 12
methods normally consist of multiple steps and use of
reagents in stoichiometric quantities (those given by The Carbon Efficiency (CE) is defined as the
the molar ratio between the various reagents in the percentage of carbon in the reagents which remains in
reaction formula) rather than catalytic (significantly the product. It takes into account the yield and
less than the stoichiometric quantities due to the fact stoichiometric ratios of the reagents actually used in
that the catalyst is reused in the reaction cycle after the reaction.
having interacted with the reactants to promote the Finally, the Reaction Mass Efficiency (RME)
reactive event). The E-factor is sometimes multiplied corresponds to the atom economy but, like the carbon
by a quotient of environmental risk (unfriendliness efficiency, it also includes the yield and actual ratios
quotient) which aims to take into consideration the between the reagents in the calculation. To a large
risk of the waste products produced; however, the extent, it represents the weight percentage of product
definition of unfriendliness quotient is very obtained compared to the weight of the reagents used.
Table 2. E-factor in the various segments of the chemical industry (Sheldon, 2000)
INDUSTRIAL SEGMENT Product quantity (t/yr) kgwaste/kgproduct
Petrochemicals and refining 106-108 0.1

Bulk chemicals 104-106 0.1-5
Fine chemicals 102-104 5-50
Pharmaceuticals 10-103 25-100

There is a substantial difference between efficiency Among the most powerful means available for
indicators and intensity or productivity indicators, in achieving the objective of a sustainable chemistry, an
that the latter not only take into account the reagents absolutely predominant role is occupied by catalysis,
but the whole mass used in the process, thus especially which has been rightly indicated as being the
highlighting the use of solvents. In this sense (and to foundational pillar of sustainable chemistry (Anastas
the extent in which the solvents and whatever else is et al., 2001). The design of new catalysts and catalytic
used in the process form a waste product), there is an systems fulfils the double objective of protecting the
affinity between intensity indicators and the E-factor environment and economic benefit. Generally
which, in turn, is essentially linked to the production speaking, using a suitable catalyst can be a powerful
of waste products. sustainability tool in the chemical industry. It enables
In addition to these indicators which are more entirely new synthetic routes to be pursued and
widely known and commonly used, and can be defined planned (which would otherwise be impossible or only
as ‘related to the mass’, analogous quantitative practicable with a minimum or limited efficiency),
evaluation parameters have been introduced. Some of aimed at the objectives and the process or product
these relate to the energy aspect, such as the total characteristics previously defined. Catalysis is able to
energy used in the process for the production of a provide numerous benefits, as illustrated in Fig. 1.
weight unit of product or, more specifically, the energy It offers the key for access to alternative raw
used in the recovery of solvents, also in terms of materials, such as those deriving from renewable
greenhouse gas equivalent (CO2). Some others relate sources. The reactions can be carried out under milder
to aspects linked to environmental risks, such as the conditions, accompanied by less significant safety
production of persistent materials, per unit of product, problems and a lower energy requirement. Less
capable of causing bio-accumulation, or the relative reactive reagents can be used, which are suitably
contribution of the process for the photochemical activated through the catalyst only when necessary, for
formation of ozone, for example: specific purposes and selectively, and they are
solvent mass POCP vapour pressure consequently intrinsically less dangerous and often less
133114 1111111112111111124 4 toxic. Through catalysis, it is possible to eliminate the
product mass POCPtoluene vapour pressuretoluene
use of stoichiometric reagents, typically characterized
wherein POCP is the photochemical ozone creation by the formation of co-products, often in the form of
potential relating to the solvent used. inorganic waste products, thus improving the atom
The use of energy indicators highlights the economy. Furthermore, a higher selectivity towards the
importance of engineering and process aspects, desired product can be reached with improved results
together with the chemical aspects, for creating a truly and with a reduction in by-products. The improved
sustainable chemistry. selectivity also leads to greater simplicity in separation
and purification, with an energy saving on the one
Instruments for sustainable chemistry hand and a reduction in the use of solvents and
By identifying the objectives of the industrial auxiliary agents on the other. It also leads to a greater
system for sustainable chemistry, the description of an purity of the product, whose toxicological
ideal process emerges which is designed for obtaining characteristics can vary significantly due to the absence
a safe and environmentally harmless product. This of toxic impurities even in a minimum concentration.
process must use safe, non-polluting, possibly In industrial practice, many catalysts have an
renewable raw materials, and not form co-products or extremely high utilization duration, also for reasons
by-products; it must have a low energy intensity and linked to their cost, especially within the context of
not require the use of solvents either in the reaction large petrochemical and bulk chemical processing,
phase or in the separation and purification phases. with the result that their use does not imply significant
Great help is obtained from the mass of disposal problems. With the use of heterogeneous
information currently available on the risks and catalysts, moreover, many of which are particularly
toxicity of products, enabling a full evaluation of the benign from a toxicological and environmental point
positive or negative impact of the chemistry that is of view, the separation of the catalyst from the reaction
being developed. In past years, this knowledge was not product is also particularly simple.
so detailed and extensive, and this may have partly Biotechnologies are, in turn, considered an
caused the environmental problems which arose then extremely promising tool for pursuing industrial
and the bad reputation that the chemical industry had sustainability (Webster et al., 1996). They are also
acquired. Conversely, from the greater information gaining ground in the production of bulk chemicals
which is currently available, the chemical community (so-called commodities), as new genetic manipulation
now has greater responsibility. techniques multiply their possibilities, overcoming the

SUSTAINABILITY
Fig. 1. Catalysis:
one of the most powerful
instruments more benign
products
for a sustainable chemistry.
milder safer
conditions reagents
controlled and targeted reactivity
CATALYSIS
high selectivity
lower lower
energy waste
consumption generation
easier
separation and
purification
economic obstacles which have long limited their Industrial biotechnology (white biotechnology)
application in the pharmaceutical world and certainly cannot be considered immune from
specialties. This application of biotechnologies sustainability problems. On the one hand, it is
appears to create fewer problems for public opinion associated with the generation of mud and waste water
than use in agriculture. to be purified from potential pollutants (phosphates,
Biotechnologies open up the field towards the use heavy metals) and, on the other, with high energy
of biomasses (starch, cellulose) and sugars deriving consumptions due to the dilution of the process
therefrom as renewable raw materials also for chemical streams. However, the preferential use of renewable
production and not only as energy vectors. In raw materials, the use and generation of highly
biorefinery (see below), biomasses are used for the biodegradable or reusable products and substrates with
combined production of chemical products with a more a low toxicity, the use of simple, highly selective
or less high added value together with energy vectors in processes carried out under mild conditions also in the
a similar way to those of a traditional refinery which production of complex molecules, and the strong
uses fuel/fossil raw material. The use of biomasses innovation potential still unexploited, all lead to the
allows a mitigation in the emission of carbon dioxide assumption that white biotechnology will take on an
into the atmosphere: as biomasses use CO2 for their increasingly important role in reducing the
own growth through photosynthesis, their use as raw environmental impact induced by chemical processes.
material does not give rise to a net increase in the CO2 Process intensification is a term which, generally
content in the atmosphere when the products reach speaking, means ‘to do more with less’ within the
their final destination in the environment. context of optimizing the industrial production
In addition to conventional productions, new uses process. It was initially conceived as a strategy for
of biomasses have become possible by introducing significantly reducing plant dimensions and,
modified microorganisms and enzymes which act as consequently, the capital invested. It can be well
biocatalysts and induce specific chemical adapted to the conception of sustainable production
transformations. The normal metabolism of a cell is processes that are characterized by an optimization of
modified through metabolic engineering techniques so the mass efficiency, reduction in energy consumption,
that it contributes to the production of the desired greater control and safety, and better product quality
chemical product. Furthermore, innovative (Jenk et al., 2004).
biochemical engineering techniques can be used for a At the basis of process intensification is the
more effective separation of the products. concept of adapting the process to the reaction and

not vice versa, by suitably modulating the Alternative raw materials

unitary operations for the physico-chemical
characteristics of the single process steps. The search for alternative raw materials is aimed at
It also aims at combining, when possible, several adopting more benign raw materials, which are
operations in a single apparatus. It can renewable or reduce risks for human beings and the
therefore be easily understood how process environment. In many cases, the selection of the raw
intensification makes wide use of the development material can represent an extremely important factor in
of innovative ideas such as membrane reactors, determining the impact of the activity on human
exchanger reactors, rotating bed or disk reactors, beings and on the environment.
reactive and catalytic distillation, high-efficiency Most chemical productions currently derive
static mixers, microstructured equipment directly or indirectly from petroleum. In the choice of
(reactors, exchangers, separators, extractors, etc.). alternative raw materials, several main trends can be
The use of microstructured components which, highlighted: a) the use of natural gas as an alternative
today, can be manufactured at low cost primary fossil source to oil; b) the use of raw materials
in a variety of metallic, polymeric and ceramic from renewable sources, of an agricultural or vegetal
materials, allows an extremely efficient mass and origin (biomasses); c) the reuse of by-products or
energy transfer. The industrial development of scraps from other processing or activities; d ) the reuse
microstructured equipment is not considered in of carbon dioxide.
terms of conventional scale-up, but rather according
to bio-mimetic criteria, through the replica of Natural gas
thousands of microstructures assembled and The use of natural gas, whose main component
interconnected in a large-scale macroproductive is methane, is an alternative which is more
unit, with the help of an integrated multiscale sustainable than oil (Rostrup-Nielsen, 2004).
design. Verified reserves of natural gas guarantee its use for
Other strong points linked to process intensification a much longer period. With natural gas, effectively
are alternative energy activation methods such as integrated systems can be constructed for the direct
sonochemical and photochemical methods, methods production of thermal and electric power, and – by
based on the use of microwaves, etc. means of direct or indirect conversion processes –
other synthetic fuels and the main commodities of
the chemical industry can be produced. Using
9.6.3 Innovation areas natural gas in combined cycle gas turbines enables
for sustainable chemistry the generation of electric power with a high yield.
Direct methane conversion processes are the object
There are numerous areas in which it is possible to of intense studies, but until now, the key step in the
operate for sustainable chemistry and these can be use of natural gas remains the production of
divided into categories. Here we will adopt the most synthesis gas (syngas), a mixture of CO and H2
commonly used distinction which refers to the obtained by partial oxidation (with oxygen) or
basic components of a chemical reaction (Anastas steam reforming (with water vapour):
and Williamson, 1996): a) alternative raw materials;
CH4 0.5O2 CO 2H2
䉴
b) alternative synthesis methods or alternative

CH4 H2O CO 3H2
䉴
reagents; c) alternative reaction conditions;

d) alternative products. Synthesis gas is a hydrogen source, also through
These four components are obviously strictly the conversion of CO to CO2 by means of the so-called
correlated with each other and the objectives in a Water Gas Shift (WGS):
varied, complex and, at times, inextricable manner. A
CO H2O CO2 H2
䉴
new synthesis method primarily aimed at improving

the selectivity or atom economy, with a reduction or it can be converted to synthetic liquid fuels such as
in the by-products through a smaller number of steps, methanol, dimethylether or synthetic fuels (synfuel)
can also envisage different raw materials and reaction for diesel and other hydrocarbon cuts obtained
conditions that are possibly more benign, such as the from the Fischer-Tropsch reaction. In addition to
limited use or absence of solvents. It is therefore not facilitating the exploitation of ‘remote gas’ (i.e. the
objectively easy to insert a real case within a specific large natural gas reservoirs located in areas far from
category, unless one of the components has such a developed regions) due to easier transportation, these
predominant importance as to make the choice simple synthetic fuels containing oxygen and, unlike many oil
and obvious. cuts, free of contaminants such as sulphur, are

SUSTAINABILITY
refinery
products
alternative gas to
fuels hydrogen hydrogen
ammonia
WGS
gas partial Fischer-

turbine natural oxidation Tropsch synfuels
electric gas syngas (FT diesel) gas to
power (methane) steam liquids
reforming
petrochemicals
olefins
methanol MTO
alternative gas to
fuels chemicals
dimethylether gasoline
MTG
Fig. 2. Use of natural gas as alternative raw material.
characterized by low polluting emissions and represent deriving from fossil sources with sugars (products
a valid answer to the new demands and regulations obtained from starch or cellulose) or with oils and fats,
relating to fuels. Like synthesis gas, methanol is a often, but not always, through the use of biosynthetic
fundamental and extremely versatile intermediate. It processes. In some cases, the product obtained from
can be transformed on acid zeolites into olefins such raw materials of a vegetable origin is only functionally
as ethylene and propylene (MTO, Methanol To Olefins similar, but chemically different from the product
process), but also into gasoline (MTG, Methanol To currently obtained from a petrochemical source: an
Gasoline process), as well as being a progenitor of example is bio-diesel, consisting of a mixture of
other important bulk chemicals such as formaldehyde methyl esters of fatty acids produced from vegetable
and acetic acid, for example. A map of the numerous oils, used in place of or in a mixture with gas oil. In
possible uses of natural gas as an alternative source is other cases, it is possible to obtain exactly the same
illustrated in Fig. 2. products, currently obtained from a petrochemical
source, from biomasses. In addition to well
Biomasses consolidated productions such as ethanol/ethylene and
In general, biomasses of a vegetable origin can acetic acid, the wide range of products which can be
represent renewable raw materials for a whole series of obtained is continually expanding. Adipic acid, for
oxygenated chemical products, in primis ethanol, but example, which is the main intermediate for the
also for methane or synthesis gas through classical production of nylon, is traditionally produced starting
gasification, fermentation or high temperature with benzene, a refinery derivative of petroleum:
pyrolysis processes, or through new developing
OH
catalytic process (for example, with the use of
homogenous catalysts based on transition metals). In OH O
this context, the use of biomasses can be well
integrated with the utilization potential of natural gas
as alternative raw material.
(
)
The use of raw materials of a vegetable origin
understandably forms the hard core of green
chemistry, a kind of green revolution which represents O O
its most strongly developing sector (Stevens and HOC(CH2)4COH
Verhé, 2004). Typical examples of the use of
renewable raw materials of an agricultural origin are An alternative raw material could be glucose, as
represented by the substitution of raw materials demonstrated in a biosynthetic pathway which does

not exist in nature, through the use of a genetically more competitive production cost (Nakamura and
modified microbial biocatalyst which transforms Whited, 2003):
glucose into muconic acid; the latter is then
hydrogenated to adipic acid (Drats and Frost, 1998): OH OH
OH
O
OPO3H2 HOCH2CHCH2OH
OH COOH HOCH2 OH
OH COOH OH
O

OH HO O O OH HOCH2CH2CH2OH
HOCH2
OH H2O3PO OH
H
OH Use of by-products
The utilization of by-products and waste-products
of other processings is a highly topical theme for
COOH sustainable development. In the oil and refining
industry, there is, on the one hand, a shift in demand
towards higher-quality fuels, subject to increasingly
HO strict specifications, such as the limitation of the
OH sulphur content, capable of guaranteeing higher
performances and lower polluting emissions during
use. On the other hand, there is a growth in the
OH utilization of increasingly heavier crude oils and
OH bituminous sands. This leads to an increased
availability of heavy hydrocarbon fractions with
reduced and economically disadvantageous
possibilities of utilization as fuel oils, when it is not
O O O O even necessary to proceed with their onerous disposal.
HOC(CH2)4COH HOCCH CHCH CHCOH Apart from traditional upgrading processes, new
developing technologies are capable of offering a better
Pyrocatechol, another industrial intermediate answer to these problems. For example, the EST
of great interest, can also be produced during technology (Eni Slurry Technology; Panariti et al.,
this biosynthetic pathway. The widely quoted 2000), based on hydrogenation in the presence of
biosynthesis of adipic acid is a possibility that has molybdenum catalysts in slurry phase and currently on
only been demonstrated on a laboratory scale, and a demonstrative plant scale, obtains the almost complete
there are doubts as to the effective current conversion of residues and non-conventional heavy
economic compatibility of this form of synthetic crude oils into higher-quality hydrocarbon cuts (Fig. 3).
pathway. A similar case, but which already seems New desulphurization technologies, in turn, allow
to have effective applicative potentialities, is the the exhaustive desulphurization of medium distillates
synthesis of 1,3-propanediol. The latter is an with a high sulphur content resistant to conventional
intermediate for a new polyester whose HDS (Hydrodesulphurization) treatment. These would
development has so far been obstructed by the otherwise not be capable of satisfying the new
excessive cost of its production carried out with specifications relating to the sulphur content aimed at
traditional methods, which involves among other reducing polluting emissions, enabling their use as
things, the manipulation of highly toxic substances high-quality fuels (Song and Ma, 2003).
such as ethylene oxide and acrolein: Desulphurization can be obtained oxidatively (ODS,
Oxidative DeSulphurization) by oxidizing the sulphur
O containing components with peracids, with hydrogen
CH2 CH2 CO,H2 H2 peroxide in the presence of ultrasounds or with
HOCH2CH2CH
O hydroperoxides, conveniently generated by treatment
with air of suitable refinery cuts: sulphur containing
H2
HOCH2CH2CH2OH molecules are thus obtained with a differentiated
polarity (sulphones) which can be easily separated from
In this case, the alternative biosynthetic method, gas oil (ULSD process, Ultra Low Sulphur Diesel; Fig. 4).
which uses a genetically modified bacterium, allows Bio-desulphurization processes by means of bacterial
the production of 1,3-propanediol from glucose at a strains, suitably enhanced for the purpose with genetic

SUSTAINABILITY
hydrogen gas
catalyst
make-up gasoline
gas oil
slurry
reactor distillation VGO
hydrocarbon
residue
solvent (propane)
deasphalting
(SDA)
DAO
recycle (asphaltenescatalyst) purge
Fig. 3. EST process. DAO, DeAsphalted Oil; SDA, Solvent DeAsphalting; VGO, Vacuum Gas Oil.
engineering techniques, are also proving to be selective crystallization, the process allows the
extremely promising (D’Addario et al., 2000). practically quantitative transformation of all
Another process of great interest which is compounds with a naphthalene structure present in
currently being developed relates to the zeolite- the starting material, into the desired product.
catalyzed production of 2,6-dimethylnaphthalene, a It is also possible to obtain high-quality feedstocks for
key intermediate of PEN (polyethylene steam cracking, consisting of C2-C5 linear alkanes,
naphthalate), a high-performance polyester. for the production of light olefins (ethylene, propylene).
Through this process, 2,6-dimethylnaphthalene is This is done by processing heavy fractions (similar to
obtained directly from naphthalene cuts of heavy those mentioned above) with hydrogen under cracking
hydrocarbon fractions with a low value of conditions, as well as the poorer-quality components of
petrochemical or refinery origin (Millini et al., pyrolysis gasoline with a high content of aromatic
2003). Through a series of successive alkylation, compounds. These poorer-quality components will
dealkylation and isomerization reactions and a have increasing difficulty in finding a place on the
gas oil from HDS desulphurized gas oil

S300 ppm S10 ppm
refinery peroxidation oxidation separation

stream to sulphones (DeSOx)
air (SOx)
Fig. 4. ULSD process.

market due to the reduction in the content of aromatic The feasibility of this reaction has been recently
products in gasoline (Ringelhan et al., 2004). demonstrated, but industrial application has not yet
been achieved, mainly due to difficulties linked to
Reuse of CO2 the unfavourable thermodynamic equilibrium. The
The reuse of carbon dioxide represents a problem synthesis of alkyl carbonates by the reaction of
of such current importance that it can be considered as alcohols with urea, which also represents a means
being a genuine trend in itself as far as the use of (indirect) for the utilization of CO2 as a raw material
by-products as alternative raw materials are concerned is, however, in a more advanced development phase.
(Aresta, 2003). The first and main opportunity for the Extraordinary interest is being shown in reforming
reuse of CO2 generally consists in the use of methane with CO2 (so-called dry reforming) as it offers
biomasses of a vegetable origin (see Chapter 6.5), a means for the direct conversion of large quantities of
as biomasses use CO2 for their own growth through CO2 to synthesis gas, even if the benefits must be
photosynthesis, allowing a virtuous sustainable cycle carefully assessed in the light of the overall energy
to be established with zero emission of CO2. balance, as a result of the reaction’s endothermicity:
There are numerous important examples of the
CH4 CO2 2CO 2H2
䉴
utilization of CO2 already in the context of large

classical processes of traditional industrial chemistry.
In reality, carbon dioxide has been adopted for many Alternative synthesis methods
years in the production of urea (used as fertilizer) and and alternative reagents
acetylsalicylic acid (better known as aspirin), in
addition to participating in the synthesis of methanol The development of new synthesis methods and the
and other processes involving the equilibrium of use of alternative reagents certainly represent the most
carbon oxides. In addition to these is the more recent interesting investigation areas with the aim of satisfying
utilization of CO2 for the synthesis of organic many of the 12 principles of green chemistry. An
carbonates, considered as building blocks of great alternative synthesis which comprises a fewer number of
interest for the creation of a sustainable chemistry due steps is definitely a step in the right direction towards a
to their benign characteristics towards human beings higher overall yield, with a consequent reduced
and the environment (see below). Alkylene carbonates formation of by-products and an improvement in the
(ethylene, propylene) are industrially produced by the E-factor. An alternative synthesis could exploit a reaction
reaction of the corresponding oxides with CO2: characterized by a better atom efficiency, especially a
R
catalytic step for example, to substitute stoichiometric
CH2 CHR reagents which are the cause of waste-products and
CO2 O O by-products. Finally, one of the key criteria in the
O
selection of alternative methods relates to reducing the
O risk (for human beings and the environment) of reagents
involved in the synthesis process.
R H, CH3, C2H5
In the presence of a different catalytic system, the Replacement of hazardous reagents

reaction evolves towards the formation of high Substances which are extremely toxic and
molecular weight aliphatic polycarbonates, characterized dangerous for the environment are widely used in the
by a high biodegradability. The amazing regularity of the chemical industry: a particularly significant example
alternation of the insertion of epoxide units and CO2 relates to the use of phosgene, a gas deriving from
allows extremely high molecular weights to be reached: chlorine, in the extremely high-scale production of
commodities such as isocyanates, intermediates for
R O the production of polyurethanes, and polycarbonates,
CH2 CHR widely-used polymeric materials. The production of
n n CO2 H OCH2CHOC
O n phosgene on a worldwide scale can be estimated as
being in the order of 6-7 million t/yr.
The homologous reaction between CO2 and The use of carbonic esters, such as
alcohols leads to the formation of alkyl carbonates. In dimethylcarbonate (DMC) and its homologues, i.e.
this way, dimethylcarbonate (DMC) can be obtained low-toxicity reagents, makes it possible to avoid the use
from methanol and carbon dioxide: of phosgene. Phosgene is highly toxic and dangerous,
and has other problems deriving from its use:
O
dependence on the chlorine cycle, the use of
2CH3OH CO2 CH3OCOCH3 H2O halogenated solvents such as methylene chloride and

SUSTAINABILITY
chlorobenzene, the formation of by-products carbonylation is carried out on liquid methanol using
and chlorinated saline waste-products. Carbonate esters, copper halides as catalysts. Fig. 5 shows a simplified
such as dimethylcarbonate and its homologous process scheme.
products, are reagents with a low toxicity and can be The dimethylcarbonate can then be easily
used in place of phosgene. Substituting the use of transformed into its higher homologous products by
phosgene in industrial practice with organic carbonates means of transesterification reactions. For example,
undoubtedly represents one of the successes of green diphenylcarbonate (DPC), which is more reactive as a
chemistry, and also of the research carried out by the carbonylation agent and therefore selected as preferred
Eni group, for many years at the forefront of promoting reagent in specific reactions, is obtained from
their industrial utilization (Rivetti, 2000a, 2000b). dimethylcarbonate and phenol:
As the production of carbonates was traditionally
linked to the use of phosgene, it was first of all O OH
absolutely necessary to develop alternative synthesis
CH3OCOCH3 2
methods which did not envisage its use (Delledonne
et al., 2001). Among those identified, apart from those
O
starting from CO2 described above, the oxidative
carbonylation of methanol to dimethylcarbonate, which OCO 2CH3OH
uses carbon monoxide and oxygen, and gives water as a
co-product, is of primary industrial importance: When a dialkyl or diarylcarbonate is used as
carbonylation agent in substitution of phosgene,
O the carbonyl group (CO) is incorporated in the
4CH3OH 2CO O2 2CH3OCOCH3 2H2O substrate, whereas the alcohol or phenol corresponding
to the carbonate is released. It is important to appreciate
In the process industrialized by EniChem for the how, in the whole sequence of reactions involved, the
production of dimethylcarbonate, the oxidative resulting alcohol or phenol can be recycled to the
CO recycle
purge
gas
purification
CO, CO2, light ends
CO2
product to CO generation unit

recovery
condenser
DMC/CH3OH
azeo
recovery
DMC, CH3OH, H2O
reactor
DMC, CH3OH recycle H2O
DMC, H2O
DMC
purification
O2
CO CH3OH DMC
Fig. 5. EniChem process for the production of dimethylcarbonate (Rivetti and Delledonne, 2003).

O CH3
CO, O2 CH3OH OCO HO C OH
CH3
OH
C
CH3 O
H2O CH3OCOCH3
O C O C
CH3 n
Fig. 6. Production of aromatic polycarbonates without the use of phosgene:

molten mass polymerization of biphenol A with diphenylcarbonate.
synthesis of the carbonate used as reagent. For Replacement of stoichiometric reagents

carbonylations carried out with organic carbonates, the The use of organic carbonates is an example of the
result is a synthesis pathway which only uses CO and O2 success with which highly dangerous reagents can be
(or CO2) and produces water alone as co-product. In the substituted by more benign reagents which perform
production of aromatic polycarbonates, for example, the the same function. Equally striking is the elimination
diphenylcarbonate, produced from dimethylcarbonate, is of stoichiometric reagents (often dangerous and the
reacted with bisphenol A in melt to produce the cause of waste products, polluting by-products and
polycarbonate. The methanol co-produced in co-products) in favour of catalytic reactions
the synthesis of diphenylcarbonate can be recycled to the characterized by an improved atom efficiency. There
synthesis of DMC. Analogously, the phenol co-produced are numerous examples of this tendency, which
in the synthesis of polycarbonate is recycled to the demonstrates the considerable power of catalysis as a
synthesis of DPC (Fig. 6). It is also interesting to note tool for a more sustainable chemistry; some of these,
that the whole cycle represents a brilliant example of a selected from the most representative and of greatest
process carried out with the total absence of solvents. industrial interest, are cited hereunder.
This synthesis method has become of considerable Typical stoichiometric reagents associated with
industrial importance: approximately a sixth of the world toxicity for human beings and problems relating to
production of polycarbonate is obtained by it. environmental pollution are those adopted in
Similarly, through the production of oxidations with metals (such as chromium and
diallylcarbonate as intermediate, the synthesis has been manganese compounds) or, even if to a lesser extent,
carried out (without phosgene) of diethyleneglycol with organic peroxides and peracids.
bis(allylcarbonate), the monomer (commercially known In this way, the oxidation of alcohols to aldehydes
as CR-39 or RAV-7) traditionally most widely used in or to ketones are still frequently carried out with
the production of high-quality optical and ophthalmic chromium trioxide, or sodium or potassium
lenses (Romano et al., 1985). dichromate in the presence of sulphuric acid. This
In addition to avoiding the use of phosgene in the produces waste products containing a toxic metal, an
above-mentioned reactions, dimethylcarbonate is also acid, and organic residues combined together that are
an excellent alternative to the use of other extremely toxic extremely difficult to dispose of. The example
and polluting reagents, such as dimethylsulphate and provided hereunder relates to the oxidation of
methyl chloride, in alkylation reactions: in this way, it is 1-octanol to octanal:
possible to selectively methylate heteroatoms (O, N, S)
to aliphatic and aromatic amines, phenols, sulphides, 3CH3(CH2)6CH2OH 2CrO3 3H2SO4
and also carbon atoms carrying activated hydrogen in
position a to nitriles, ketones, esters, sulphones, etc. 3CH3(CH2)6CHO Cr2(SO4)3 6H2O

SUSTAINABILITY
The same reactions can be carried out using air in A historical method for the industrial preparation
the presence of a variety of catalysts, such as for of hydroquinone (1,4-dihydroxybenzene) consists in
example, 2,2,6,6-tetramethylpiperidine-N-oxide the oxidation of aniline with manganese dioxide to
(TEMPO) combined with ruthenium complexes give quinone, followed by the reduction of the latter
(Sheldon, 2000): with iron. The process gave as co-products ammonium
sulphate and iron oxide in stoichiometric quantities
RuCl2(Ph3P)3 compared to hydroquinone, and a quantity of
2CH3(CH2)6CH2OH O2
CH3 CH3 manganese sulphate equal four times this
H3C N CH3 stoichiometric value:
.
O NH2
O
2 4MnO2 5H2SO4
2CH3(CH2)6CH 2H2O
O
The use of 4-hydroxy-TEMPO as catalyst for the
production of bisnoraldehyde by means of oxidation Fe, H2O
2 (NH4)2SO4 4MnSO4 4H2O
with sodium hypochlorite of the corresponding alcohol
represents the keystone of a new and more benign O
commercial synthesis method of progesterone (Hewitt,
1998). This method has replaced a prior process based OH
on the oxidation of stigmasterol in two steps
2 FeO
(oxidation according to Oppenhauer with aluminum
ter-butoxide and cyclohexanone followed by OH
ozonolysis and reduction with zinc/acetic acid),
reducing aqueous refluents 5 times and organic waste The same product, together with the 1,2 isomer
10 times. The new method also allows a more effective (pyrocatechol), can be obtained directly from phenol
use of the raw material at the start of the process: without the use of metals and without a significant
generation of inorganic by-products, using hydrogen
soybean peroxide as an oxidant, which gives only water as
sterols
co-product:
(100% ) (15%)
OH OH OH
OH TS-1 OH
H2O2 H2O
OH
HO
This process represented the first industrial
cyclohexanone application of titanium silicalite (TS-1), a catalyst of
Al(OtBu)3 the zeolite group with an MFI structure, synthesized
for the first time and developed by research
OH
laboratories of the Eni group as a selective oxidation
H3C CH3 catalyst in numerous applications (Perego et al.,
NaOCl
H3C N CH3 2001). Among other applications subsequently
developed for titanium silicalite, mention should be
O
O made of the ammoximation of ketones with NH3 and
H2O2, especially of cyclohexanone to give
1. O3
cyclohexanone oxime, an intermediate in the
2. Zn/CH3COOH
production of Nylon 6, also recently attaining
industrial exploitation (Petrini et al., 1996). The
H
conventional technology used in the production of
O cyclohexanone oxime (Raschig process) creates the
problem of a high co-production of ammonium
sulphate (approximately 2.8 kg/kg), which gives rise
to onerous disposal problems:

O Cl2
CH3CH CH2
H2O
.
NH2OH H2SO4 2NH3
Cl OH
NOH NaOH
CH3CHCH2OH, CH3CHCH2Cl
(NH4)2SO4 H2O
NaOH CH3CH CH2 NaCl
It is also jeopardized by the complexity of the O
operating cycle, linked to the synthesis of the
intermediates involved, especially The process via chlorohydrin is jeopardized by a
hydroxylamine, and to the inorganic raw series of problems, with evident implications of an
materials used (hydroxylamine sulphate is environmental nature, such as the formation of
produced from NH3, CO2 and SO2), and the inorganic and organic chlorinated by-products. A
consequent problems relating to polluting waste product is formed, equal to approximately 40
emissions (NOx, SOx). The ammoximation times the volume of the epoxide produced, consisting
process represents a radical innovation of a diluted solution of sodium or calcium chloride
in the sector. The term ammoximation and organic chlorinated residues. The epoxidation
indicates that the production of oxime is process of propylene with H2O2 catalysed by titanium
carried out directly starting with ammonia: silicalite, on the other hand, gives water only as co-
the process is, in fact, based on a catalytic product (Clerici et al., 1991):
reaction between cyclohexanone, ammonia
TS-1
and hydrogen peroxide which, on the CH3CH CH2 H2O2 CH3CH CH2 H2O
one hand, completely eliminates the critical
O
aspects linked to the production and use of
hydroxylamine and, on the other, the It is an improvement even when compared to
co-production of sulphates: processes via hydroperoxides, which give styrene or
MTBE (methyl-tert-butylether) as co-product, as it
O NOH eliminates the necessity of recycling or placing the
TS-1 co-product on the market:
NH3 H2O2 2H2O
CH3
O2
Another ammoximation process catalysed by R-H R – OOH R C MTBE
titanium silicalite of great industrial importance is CH3
used in the production of paracetamol:
R– OOH
CH3CH CH2 CH3CH CH2 R – OH
CH3 CH3 O
O
C O C NOH NHCCH3
CH styrene
TS-1 H
NH3 H2O2 CH3
OH OH OH Similar problems, relating to marketing the acetone

co-produced or recycling it as an alkylating agent of
New processes in the development phase for benzene, after reduction to isopropanol, are linked to
the production of propylene oxide and phenol are the current production process of phenol, via cumene
also extremely important. Propylene oxide is a (Girotti et al., 2003):
basic intermediate of the chemical industry, used
OOH
for producing a long series of other products and
materials, in primis polyether polyols devoted to CH(CH3)2 C(CH3)2
the production of polyurethanes. In the CH3CH CH2 O2 H
conventional process, propylene is reacted with
chlorine in an aqueous solution, producing a
mixture of chlorohydrins, from which propylene OH O
oxide is released, by treatment with lime or
caustic soda: CH3CCH3

SUSTAINABILITY
Also in this case, the direct oxidation of benzene to have high catalytic activities, and normally have a long
phenol with H2O2 catalysed by titanium silicalite, duration and are easy to regenerate, so that problems
currently in the development phase, allows these associated with their disposal are practically zero.
problems to be solved (Balducci et al., 2003): Alkylation is a very important refinery process
which allows isobutane and C3-C5 olefins to be
OH
converted to C7-C9 branched paraffins with a high
TS-1
H2O2 H2 O octane number, ideal components for gasoline:
CH3CH(CH3)2 CH3CH CHCH3
An alternative method for the direct synthesis of
phenol from benzene uses nitrous oxide (N2O) as CH3
oxidant and a ZSM-5 zeolite containing iron as
(CH3)3CCHCH2CH3
catalyst (Panov, 2000):
OH This reaction is traditionally catalysed with
concentrated sulphuric acid or with hydrofluoric acid,
Fe-zeolite
N2O N2 with an installed productive capacity which is more or
less equally distributed. These are highly corrosive
Unfortunately, the cost of a production ad hoc of substances which create considerable environmental
N2O is too high and the only plausible scenario for the and safety problems if they spill, in addition to
application of this process envisages the reuse of N2O generating large quantities of inorganic by-products
by-product from production plants of adipic acid (HF forms stable aerosols at a ground level, whereas in
(intermediate of nylon). the case of H2SO4, the production of spent acid to be
The synthesis of phenol by the selective disposed of reaches 70-100 kg per tonne of alkylate).
hydrodeoxygenation (HDO) of polyphenols such as Industrial alkylation processes are currently
catechol, appears to be potentially quite interesting, available that are competitive with traditional
especially with the prospect of producing the latter technologies, which use a variety of solid acid
from renewable raw materials such as lignocellulose catalysts, from large-pore zeolites, with a Y-type
biomasses: structure, normally containing metals with a
OH hydrogenating function, to Lewis or protic acids such
as aluminum trichloride or trifluoro methanesulphonic
H2 H2O acid supported on porous substrates such as alumina
OH (Hommeltoft, 2001). The use of these processes is
capable of eliminating most, if not all, of the
New catalysts disadvantages of processes based on liquid acids.
An extremely interesting trend which enjoys Friedel-Crafts reactions (from the name of their
considerable success is the substitution of those discoverers), i.e. alkylation and acylation of aromatic
catalysts which – as a result of their poor catalytic compounds in the presence (prevalently) of
activity (or duration of their catalytic life) and/or due aluminum trichloride (AlCl3), form a very important
to the difficulty or impossibility of separation, group of reactions that belong to a wide range of
work-up and recycling – are used in massive quantities sectors of the chemical industry, from petrochemicals
and are also characterized by a high risk for human to fine chemicals and pharmaceuticals productions.
beings and the environment. Numerous acid catalysts The use of AlCl3, however, is not without problems.
widely used on an industrial scale such as sulphuric In alkylation reactions, it can be used in a catalytic
acid, hydrofluoric acid and aluminum trichloride quantity but it cannot be recovered at the end of the
belong to this category. Exceptional results in enabling reaction, with the result that the quenching of the
their substitution have been obtained through the use catalyst with water creates significant liquid and
of solid acid catalysts, especially synthetic zeolites. solid waste products containing aluminum and
These silico-aluminates can be easily obtained in acid chlorine. It is mainly in acylation reactions, however,
form and have orderly porous crystalline structures, where AlCl3 must be used in a quantity which is even
which form ideal matrixes for directing and higher than the stoichiometric value (up to two times)
accelerating chemical reactions and also making them that after the quenching of the catalyst, there is an
selective. As zeolites are heterogeneous catalysts, their enormous production of waste products. The use of
use minimizes problems linked to the separation of the zeolites in substitution of traditional catalysts for the
catalyst from the medium and reaction products. alkylation of aromatic compounds is now a
Zeolites are configured as inert solids from a well-consolidated reality and is widespread in large
toxicological and environmental point of view, they petrochemical processes. Their use, for example, has

become prevalent in industrial synthesis reactions of which is extremely toxic and corrosive, in turn,
ethylbenzene, an intermediate in the production of requires the use of strict safety measures, and
styrene, and cumene, an intermediate in the extremely costly equipment and materials. Beta
production of phenol. In these reactions, large-pore zeolite is also adopted as catalyst in the acylation of
zeolites, such as beta zeolite, have substituted, as other industrially important aromatic ethers such as
alkylation catalysts of benzene with ethylene and anisole (to p-methoxy acetophenone) and veratrole.
propylene, aluminum trichloride and phosphoric acid The acylation catalysed by the zeolite uses acetic
(H3PO4) supported on silica, respectively (Perego anhydride as acylation agent in the absence of
and Ingallina, 2002). In an ethylbenzene plant with a solvent and allows a higher yield (from 85-90% to
capacity of 500,000 t/yr, the production of an over 95%). The classical process, on the contrary,
aqueous effluent of aluminum hydroxide in the order uses acetyl chloride combined with more than one
of several thousands of t/yr is thus avoided, whereas equivalent of AlCl3 and a chlorinated hydrocarbon as
in the production of cumene, the generation of solvent. The new process thus avoids the generation
organic aromatic by-products is reduced by at least of hydrochloric acid (HCl) deriving from both the
20 times, and the necessity to periodically dispose of use of aluminum trichloride and acetyl chloride
the catalyst in landfills is practically zero: (as well as the synthesis of the latter). The classical
process generates 4.5 kg of aqueous effluent per kg
beta zeolite CH2CH3 of product, containing aluminum compounds, HCl
CH2 CH2 (styrene)
or its salts and residues of chlorinated hydrocarbons.
The catalytic alternative process generates only
beta zeolite CH(CH3)2 0.035 kg of aqueous effluent per kg of product
CH3CH CH2 (phenol) (i.e. more than 100 times less) containing less than
1% of organic compounds, mainly acetic acid. The
As far as acylation reactions are concerned, the use product is isolated by the simple filtration of the
of beta zeolite allows the substitution of aluminum catalyst (which can be recycled) and distillation, with
trichloride or hydrofluoric acid in the synthesis of the result that the number of unitary operations is
2-acetyl-6-methoxy naphthalene, an intermediate for reduced from 12 to 2 (Sheldon, 2000).
the production of naproxen (the well-known Also in nitration reactions of aromatic compounds,
antipyretic agent, a non-steroid analgesic the use of zeolites as catalysts, as also other solid acids
and anti-inflammatory drug) and in the synthesis of (for example Nafion, a sulphonated perfluorinated
isobutylbenzene of 4-isobutyl acetophenone, an polymer), represents an alternative to the use of the
intermediate of the equally well-known ibuprofen sulphonitric mixture (HNO3/H2SO4) traditionally
(Andy et al., 2000): adopted. In addition to eliminating the use of sulphuric
beta zeolite acid with consequent problems of disposal, the
(CH3CO)2O formation of polynitrated products is significantly
H3CO reduced, and in particular, with the use of beta zeolite,
COCH3 a high selectivity towards the para isomer is obtained
CH3COOH (Bernasconi et al., 2004):
H3CO
CH3
beta zeolite
CH2CH(CH3)2 CH2CH(CH3)2 HNO3 (CH3CO)2O
beta zeolite
(CH3CO)2O CH3COOH CH3
COCH3 2CH3COOH
As already mentioned, this avoids the use of a NO2

higher quantity of aluminum trichloride than the
stoichiometric value, necessary as a result of the Finally, one of the most striking examples of the
strong complexing of AlCl3 with the carbonyl industrial use of a zeolite as solid acid catalyst relates
compound formed. Furthermore, the subsequent to the substitution of oleum (a mixture of concentrated
hydrolysis process necessary for decomposing this sulphuric acid and sulphur trioxide) used in a large
intermediate, which generates large quantities of quantity in the Beckmann rearrangement of
inorganic by-product and is the cause of onerous cyclohexanone-oxime to caprolactam (Ichihashi and
separation processes, is also avoided. The use of HF, Sato, 2001):

SUSTAINABILITY
N OH O O
NH
H2SO4 2NH3 (NH4)2SO4 CCH3
(CH3CO)2O ClCH2COOC2H5
The new reaction completely avoids the AlCl3 NaOC2H5

1 2
co-production of 1.3-1.6 kg of ammonium sulphate (CH3)2CHCH2 (CH3)2CHCH2
per kg of caprolactam produced, deriving from the
neutralization of oleum: CHO
COOC2H5
O CHCH3
N OH O H, H2O NH2OH
silicalite MFI NH CH3
3 4
(CH3)2CHCH2
(CH3)2CHCH2
The coupling of the ammoximation process of
cyclohexanone to cyclohexanone-oxime, indicated CH NOH CN COOH
above, with the new catalytic rearrangement process CHCH3 CHCH3 CHCH3
has opened up the way to a production of H, H2O
caprolactam which is completely free of the
5 6
co-production of salts.
(CH3)2CHCH2 (CH3)2CHCH2 (CH3)2CHCH2
Syntheses with a fewer number of steps
In many cases, the setting up of an alternate A new synthesis has been developed and used on
synthesis strategy aims not only at exploiting an industrial scale (it currently covers approximately
reactions characterized by a better atom efficiency 25% of the whole world production of ibuprofen),
and the use of less hazardous reagents, but also at which envisages only three steps, with a doubling of
reducing the number of steps necessary for the atom efficiency to at least 80% and a consequent
obtaining the product. A fewer number of steps significant reduction in the quantity of by-products
favours a higher overall yield and a reduction in the generated (Cann and Connelly, 2000):
quantity of by-products.
O
The search for alternative synthesis pathways has
led to the development of logic protocols as a basis for CCH3
computerized programs, based on the observation that (CH3CO)2O H2
the number of possible synthesis methods for objective HF Ni-Raney
molecules with even a modest complexity is normally 1 2
huge (Hendrickson, 1996). It has been observed that (CH3)2CHCH2 (CH3)2CHCH2
within the range of these programs, the most reliable OH COOH
selection criteria of the synthesis strategy are those
CHCH3 CHCH3
simply based on the number of steps, as predicting the
yields is often so inaccurate as to be totally useless. CO
The best synthesis methods are therefore normally the Pd(II)
shortest. 3
(CH3)2CHCH2 (CH3)2CHCH2
It is not surprising that the most significant
examples of the reduction in the number of steps in The new synthesis, which in current industrial
complex synthesis procedures are mainly found in practice still contemplates the use of HF as catalyst
the pharmaceutical, or fine chemical and specialty of the acylation step, will be able to obtain further
sectors. Ibuprofen has already been mentioned as benefit from the use of the zeolites described
being one of the most widely used pharmaceutical above. Another alternative synthesis which has
aids among anti-inflammatory, analgesic and proved to be valid up to a pilot scale for ibuprofen,
antipyretic drugs. The traditional synthesis of as also for the homologous arylpropionic acids
ibuprofen requires six steps with the use of large ketoprofen and naproxen, exploits the use of
masses of solvent and corrosive reagents, used in a dimethylcarbonate as reagent, with yields
stoichiometric quantity. A calculation of the atom exceeding 99%. Similarly, again through the use of
economy indicates that only 40% of the atoms dimethylcarbonate, a synthesis strategy has been
present in the raw materials is incorporated in the elaborated which allows the production of the
product: wide-range antibiotic cyprofloxacin using three

reaction steps less compared to the traditional elimination (“the best solvent is no solvent”), with
method (Rivetti, 2000b). considerable benefits also from an economic point of
In the pharmaceutical industry, there are generally view and for the simplicity of the processes. It is not
numerous and widely recognized examples of by chance that many consolidated processes of the
productions of active principles which have benefited bulk chemical industry operate without solvents,
from the identification and development of alternative generally in gaseous phase. This tendency is
synthesis strategies; they are characterized by a lesser expanding as demonstrated by recent processes for the
complexity, greater efficiency, elimination of toxic polymerization of ethylene and propylene in a fluid
reagents and auxiliaries, reduction in the use of bed reactor in gas phase or the polymerization of ABS
solvents, and quantity of waste products generated (Acrylonitrile Butadiene Styrene) in a fluid mass.
(Dunn et al., 2004). There is ample space for the substitution of
An extremely important role in the definition of a solvents with other less toxic, volatile and flammable
synthesis characterized by a lesser complexity and products. For the washing of metal surfaces,
greater efficiency is played, on the one hand, by the chlorinated solvents, for example, can be substituted
use of bio-catalysis and fermentative processes and, on by: a) esters, such as dibasic esters (a mixture of
the other, by the use of chiral catalysts for the methyl adipate, glutarate and succinate); b) methyl
stereo-selective synthesis of the desired isomer esters deriving from vegetable oils (also used as fuels
(asymmetrical catalyst). Well-known examples in this for motor vehicles, the well-known biodiesel);
respect are L-dopa, l-menthol and (S)-metolachlor. c) dibutyl carbonate; d ) naturally occurring terpenes
These two aspects are often conveniently combined in (limonene); e) or finally by water-based formulations
the use of enzymatic catalysis. containing surface-active agents. We will now examine
the role of the benign solvents par excellence, i.e.
Alternative process conditions water and carbon dioxide, either liquid or under
supercritical conditions; and also other innovative
The conditions used in synthesis processes of solvents, such as ionic liquids.
chemical products can have important environmental These are only a few examples of the imposing
and safety drawbacks: risks associated with severe transformations which are taking place in the field of
reaction conditions, high energy consumption and solvents; they involve not only the production and
harmful emissions. Many solvents (so-called VOCs, processing area but also, and above all, the
Volatile Organic Compounds), used in reactions and formulation of products available to users, from
separation/purification operations, substantially products for personal and household hygiene to paints
contribute to polluting air and water. There are and varnishes (just consider, for example, water-based
consequently well-founded reasons for widely directing paints).
the search for alternative process conditions towards The most benign and economic solvent is naturally
eliminating the use of solvents or developing the use of water. Even if it is the main medium of biochemical
alternative benign solvents. A study of reactions in reactions in living systems, water is traditionally
aqueous, biphasic systems (which include, in addition to considered as being a solvent which is difficult to use
traditional aqueous-organic systems, ionic liquids and in chemical reactions. Many reagents and organic
perfluorinated solvents) and also supercritical systems, products, as also numerous homogeneous catalysts
especially supercritical CO2, forms part of this trend. A based on complexes of transition metals, are insoluble
second tendency in the search for alternative process in water (even if there are significant and important
conditions relates to attempts at process intensification, exceptions), and the recovery of the products from
already mentioned above. Process intensification aims aqueous solutions is generally quite onerous. Water,
to allow the use of milder reaction conditions and a moreover, can be relatively reactive towards organic
more selective activation, and it includes alternative molecules and is capable of inhibiting numerous
energy activation methods, such as the use of reactions. In spite of this, there are recent examples in
ultrasounds and microwaves; greater attention towards which this traditional negative outlook has been
more classical energy sources, such as those used in completely reversed, as in the case of the use of an
photochemistry and electrochemistry. These aqueous medium in Diels-Alder reactions (Breslow,
unconventional activation techniques are often ideal for 1998) and in Barbier-Grignard organometallic
enabling reactions to be carried out without solvents. syntheses (Li, 1998; Paquette, 1998), a group of
reactions of considerable synthetic utility, e.g. in the
Alternative solvents chemistry of carbohydrates.
The radical solution to the problems created by the Under near-critical conditions (T250-350°C,
use of solvents obviously lies in their complete P5-10 MPa), the solvency characteristics of water

SUSTAINABILITY
become similar to those of organic solvents such as this prospect, an increasingly important role is being
ethyl alcohol or acetone. Its dielectric constant played by multiphase processes. Processes based on
decreases from 80 to 20, and its density, from 1 to 0.7. phase transfer catalysts in a heterogeneous aqueous-
This ensures that almost all organic compounds which organic biphase environment were introduced over
are normally insoluble can be dissolved under these thirty years ago, and include consolidated examples
conditions and reacted in homogeneous phase in of industrial application. In these processes, the
water, thus becoming an excellent reaction medium. aqueous phase acts as a reserve for the generation of
The lowering of the temperature and pressure at the reactive inorganic or organic anions, which migrate
end of the reaction forms a simple separation method into the organic phase containing the reagents and
as a result of a reduction in the induced solubility, catalyst, where the reaction takes place (Makosza,
allowing easy recovery of the products. Furthermore, 2000). The catalyst (PCT, Phase Transfer Catalyst) is
under these conditions, water becomes substantially normally a quaternary ammonium or phosphonium
dissociated, allowing acid- or base-catalysed reactions salt, which is a source of lipophilic cations. As such,
to be carried out without the actual addition of acids or it is capable of transferring the anion into the organic
bases, and without the consequent co-production of phase through the formation of an ionic couple, thus
salts resulting from their neutralization. Examples of allowing the reaction to proceed, which would
the use of water as solvent under near-critical otherwise not be able to take place. The use of this
conditions are classical base-catalysed reactions such type of catalysis in an aqueous-organic biphase
as aldol and Claisen condensation, and the Cannizzaro system avoids the necessity of having to resort to the
reaction and Friedel-Crafts acylation, carried out use of aprotic polar solvents which are often toxic,
without the use of Lewis acids as catalysts such as dimethyl formamide (DMF) or dimethyl
(Nolen et al., 2003). An example is the synthesis of sulphoxide (DMSO), and allows better yields,
anthraquinone: selectivity and reaction rates.
Selective oxidations with hydrogen peroxide in an
O O
aqueous-organic biphase medium, in which the
H2O
activation of the H2O2 is catalysed by a mixture of
275°C phosphate (or arsenate) and tungstate anions, become
O
O possible through the use of phase transfer catalysis
OH
(Kozhevnikov, 1998). This selective oxidation method
The use of water under supercritical conditions has been applied on a commercial scale for the
(T 374°C, P22 MPa) is at the basis of processes in production of 1,2-epoxydecane and isobutyl
which water acts as both reagent and solvent for 3,4-epoxybutyrate, a key intermediate in the synthesis
destroying organic waste products by total oxidation; of the nootropic drug Oxiracetam:
for the selective oxidation with oxygen of alkyl
aromatic compounds (such as p-xylene to terephthalic O
2 3
WO4 /PO4
acid) with MnBr2 as catalyst, which avoids the use of CH2 CHCH2COCH2CH(CH3)2 H2O2
acetic acid as solvent; for the recycling of PCT, H2O
condensation polymers such as polyurethanes (PU) or O HO
polyethyleneterephthalate (PET) through conversion CH2COCH2CH(CH3)2
back into the starting monomers. This latter process is N O
O
applied commercially for the recovery of toluene CH2CONH2
diamine from residues of the production of TDI
(toluene diisocyanate): On the wave of successes of phase transfer
catalysis, reactions catalysed by complexes of
CH3 CH3 transition metals have been carried out in an
NCO supercritical NH2 aqueous-organic biphase system, in which the catalyst
2H2O 2CO2
conditions is situated in the aqueous phase where the reaction
NCO NH2 takes place. A simple phase separation is then
sufficient for isolating the product from the catalyst
The identification of alternative solvents not only which can be easily recycled. The most prominent
aims at using solvents with a low toxicity for human example of this method is the hydroformylation of
beings and the environment, but also at defining propylene to butyraldehyde (Kohlpaintner et al.,
alternative process conditions which enable the easy 2001). The catalyst, a rhodium phosphine complex, is
recycling of the reagents, catalyst and solvent and the made hydrosoluble by the insertion of sulphonic
simple separation of the product (Keim, 2003). With groups in the phosphine ligand:

CATIONS ANIONS
BF4 PF
6 SbF6
R1
N H
N R fluoborate hexafluorophosphate hexafluoroantimonate
R2 4 N N
R3
R H CF3SO
3 CH3 SO3
ammonium pyridinium pyrazolium
mesylate tosylate
R1
NO CF3COO
P R N
N
3
R2 4 R1 R2 N nitrate trifluoroacetate
R3
R1 R2
phosphonium imidazolium pyrrolidinium AlCl
4 Al2Cl
7
R C3-C16 chloroaluminates
Fig. 7. Ionic liquids.
O generally a salt of a quaternary ammonium or

RhLn phosphonium cation with a variety of anions, which,
CH3CH CH2 CO H2 CH3CH2CH2CH
H2O although being of an ionic nature, is liquid or
low-melting due to the size of the ions and the low
NaO3S SO3Na molecular symmetry (an ionic liquid is conventionally
L P distinguished from a molten salt when it has a melting
point lower than 100°C). A material of this type is in
liquid form within a temperature range which can
SO3Na extend to values in the order of 200 and up to 300°C
(for water, this range is known to be 100°C). Ionic
Systems based on perfluorinated or highly liquids are now commercially available (Fig. 7).
fluorinated solvents have been recently developed Ionic liquids as such are characterized by zero
(FBS, Fluorous Biphase Systems), which overcome vapour pressure, and their structure can be
the limitations of aqueous-organic systems. Such programmed so as to provide marked hydrophilic and
limitations are linked to the fact that the reaction has hydrophobic properties. This characteristic can be
to be carried out in an aqueous medium, whilst exploited for the generation of biphase systems for
maintaining the characteristics which make them both water and apolar organic phases which favour the
interesting from the sustainability perspective, in separation of the reaction product.
primis, the easy separation of the products (Horvath, The use of ionic liquids has been studied in an
1998; Curran and Lee, 2001). Solvents of this type are extremely wide variety of reactions, which include
generally non-toxic and biologically compatible. Their among the most significant examples, Friedel-Crafts
miscibility with products and organic solvents can be reactions, hydrogenation, oxidation, hydroformylation,
modulated in relation to the temperature, so that in dimerization and oligomerization of olefins. Ionic
many cases, homogeneous solutions can be obtained in liquids generally dissolve most complexes of transition
the reaction phase, subsequently causing de-mixing by metals extremely well and can therefore be easily used
cooling into two phases to facilitate the separation of in homogeneous catalysis. Other alternative solvent
the product and recycling of the catalyst. systems, such as carbon dioxide or perfluorinated
Because ionic liquids have similar qualities, great solvents, often suffer from a low solubility of metal
interest has recently been shown in their use, among complexes and require the synthesis of specifically
the neoteric solvents (Wilkes, 2002), even if their designed ligands.
characteristics of toxicity and recycling stability, as In the 1980s and early 1990s, a foremost process in
well as problems relating to their production cost are the study of the use of ionic liquids was the conversion
still controversial. An ionic liquid is a compound, of synthesis gas into oxygenated organic compounds

SUSTAINABILITY
n-octenes catalyst:
Ni complex
ionic liquid:

H3C N N C4H9
light olefins
catalyst AlCl
4
in ionic liquid
(propylene, butenes, etc.)
1-butyl-3-methylimidazole
tetrachloroaluminate
Fig. 8. Difasol process.
such as ethylene glycol, acetic acid, and alcohols on a the form of anions BF
4 , PF6 , etc. enabled their interesting
molten catalytic system containing ruthenium in which characteristics to be exploited in other reactions of
ruthenium complexes are dispersed together with olefins such as hydrogenations, hydroformylations and
co-catalysts in low-melting quaternary ammonium and Diels-Alder reactions or as extraction solvents. An
phosphonium salts. More recently (Olivier, 1999), a interesting example relates to the elimination of
dimerization process of light olefins, such as propylene compounds containing S and N from gasoline, gas oils
and butenes was developed, catalysed by nickel carried and other refinery products by extraction with ionic
out in double phase, using an acid ionic liquid which liquids, such as 1-butyl-3-methyl imidazole
acts both as solvent and co-catalyst (Difasol process). octylsulphate. These have good extraction properties
The cationic nickel catalyst is stabilized in the ionic also for sulphur containing compounds which are
phase without the necessity of additional ligands, difficult to eliminate by means of
whereas the reaction products (C6-C10 olefins) form a hydrodesulphurization, such as dibenzothiophene and
second less dense phase which can be easily separated. its alkyl derivatives (Esser et al., 2004).
In this way, there is a higher catalytic activity, a The use of carbon dioxide in liquid form or under
reduced consumption of catalyst, and improved supercritical conditions (Tc31.1°C, Pc7.38 MPa)
selectivity to the desired dimers compared to the also represents an alternative to the use of traditional
traditional process in homogeneous phase (Fig. 8). solvents (Aresta, 2003). Carbon dioxide is available in
Analogously, isobutene can be polymerized to high large quantities, it is not toxic or flammable, and is
molecular weight polyisobutene in an acid ionic liquid, inexpensive. Its solvent properties can be suitably
such as an alkylmethylimidazole or N-alkylpyridine modulated by varying the operating pressure, i.e. the
chloroaluminate. Polymerization in ionic liquid can density, in this way significantly influencing the
offer a series of advantages compared to the traditional solubility parameter. In spite of this, CO2 as a solvent
process which uses aluminum trichloride: the polymer always maintains an extremely low polar nature (its
forms a separate layer and does not require subsequent solvent properties can be compared to those of a
aqueous washings for purification. The catalyst can be hydrocarbon such as hexane), and it is therefore not
recycled, and undesired secondary reactions, such as able to dissolve salts or highly polar polymers and is
isomerization, are kept under control without the not suitable for ionic reactions or reactions catalysed
necessity of an alkaline quenching of the reaction. by ionic catalysts. In these cases, resort is made to the
The processes described make use of ionic liquids use of phase transfer agents or lipophilic ligands and
in the form of chloro-aluminates, with acid counter-ions. Another limitation may be that carbon
characteristics, the first to be used in Friedel-Crafts dioxide is an electrophilic reagent of a slightly acidic
reactions and di/oligo/polymerization, nature and is capable of interacting with basic
alkylation reactions or the isomerization of olefins. substances. In practice, the most appropriate reactions
The subsequent development of neutral ionic liquids in are those involving gases with a poor solubility in

conventional solvents, such as hydrogen and oxygen. administration of heat or the use of traditional reagents
This exploits their complete miscibility with CO2 and catalysts) is generally considered an instrument of
under supercritical conditions and, in the case of sustainable chemistry with an extremely high
oxygen, also the fact that as the CO2 molecule is at its potential, even if it has still not been adequately
maximum oxidation state, it cannot be further oxidized studied and exploited. Among these activation
(Morgenstern et al., 1996). methods, various relatively known and consolidated
A consolidated industrial application of carbon techniques can be mentioned on the one hand, such as
dioxide under supercritical conditions (or liquid) is the the use of electricity (electrochemistry) and light
extraction of caffeine (and also other natural and (photochemistry); and emerging borderline
pharmaceutical active principles); more recent techniques, on the other, such as the use of
applications or those in the pre-marketing phase are microwaves and ultrasounds (sonochemistry).
the washing of metallic parts, spray varnishing, All of these methods have various common
the production of silica aerogels and fine powders, the characteristics which make them potentially
deposition of thin films and dry cleaning of clothes, interesting. They can activate molecules, for example,
substituting trichloroethylene. in an extremely specific manner, allowing reactions to
The industrial use of carbon dioxide under take place which would otherwise be impossible,
supercritical conditions as reaction solvent in improving the selectivity, allowing the use of milder
substitution of freon in the polymerization of reaction conditions; they can avoid the use of reagents
tetrafluoroethylene has been announced, but there is and catalysts, eliminating problems relating to
no confirmation of the plant construction. More separation and the generation of by-products; they can
recently, its use has replaced acetone in a continuous significantly reduce the reaction times. They are
multipurpose plant for the hydrogenation of particularly suitable for solvent-free reactions or
isophorone to trimethylcyclohexanone with palladium reactions using new or benign solvents such as ionic
catalysts, guaranteeing quantitative conversions and liquids or water. The economic aspects and difficulties
selectivity (Licence et al., 2003). of the industrial scale-up, however, which have
Other reactions usefully studied in supercritical CO2 different characteristics compared to the scale-up of
are hydroformylation, etherification and esterification, conventional processes, have often been the cause of
Friedel-Crafts reactions and various kinds of an under-utilization of even the most consolidated
polymerizations. The latter ones (as for extractions) take activation techniques.
advantage of the low viscosity, high diffusivity and Electrochemical techniques, for example, are
ability to permeate the polymeric solid with capable of providing many benefits from the
plasticization of the precipitated polymer, as well as the sustainability point of view (Matthews, 2001).
ability not to leave residues of solvent in the polymer. Electrodes can be seen as heterogeneous catalysts
This leads to an improvement in the yields and molecular which can be easily separated from the reaction
weights in both radical polymerization and products. Electrons can be considered as a reagent
poly-condensation reactions. An important example is which can be used with a 100% atom efficiency and
the use of supercritical CO2 in the production of aromatic under rather mild conditions of use. Oxidation and
polycarbonates carried out in melt or in the solid state. reduction reactions (characterized by the loss or gain
Carbon dioxide under supercritical conditions of electrons by a molecule) are ideal because they are
represents a potential substitute for organic solvents in activated even by the sole passage of an electric
biphase reactions with water, such as phase transfer current, without the necessity of additional reagents.
reactions. In the same way, the combination of Electricity can therefore be used for substituting toxic
supercritical CO2 and (per)fluorinated solvents or ionic stoichiometric reagents, as in oxidations traditionally
liquids can offer special advantages: neoteric solvents performed with halogens.
contain the catalyst, whereas the reaction products are A wide-scale use of electrochemistry can only
extracted in supercritical CO2. happen with a significant and generalized reduction in
Finally, carbon dioxide under supercritical the cost of electric energy. In a scenario of this kind,
conditions can be a particularly advantageous reaction significant prospects could be opened up for the reuse
medium because it also acts as reagent, as in the of carbon dioxide through electrochemical techniques,
aforementioned syntheses of organic carbonates and as in the synthesis of methanol (Sánchez-Sánchez
polycarbonates obtained from CO2. et al., 2001).
Photochemistry also paves the way towards
Alternative activation methods potential scenarios linked to the utilization of visible
The use of alternative activation methods of light as a source of energy and materials, following
chemical reactions (different from the normal mimetic processes of photosynthesis. In more concrete

SUSTAINABILITY
terms, light is an activation system which does not improvements in the mass transfer and phase transfer
leave residues to be removed after the reaction. It is effects. Beneficial results can be obtained such as: a) a
capable of activating molecules in an extremely reduction in the reaction times; b) increased yields;
selective manner and promoting different reactivities, c) milder reaction conditions; d) a change in the reaction
typically radical reactivity, and new reactions, mechanisms with the establishment of modified or
otherwise extremely difficult or even impossible, such completely different reactivities; e) improved
as certain isomerizations and cyclo-additions of efficiency of the reactions carried out in water or
olefins which involve thermally prohibited transition under multiphase conditions.
states (Albini et al., 2000).
The activation of molecular oxygen also becomes Alternative products
possible under much milder conditions and providing
better reaction selectivities: it has been demonstrated One of the fundamental objectives of sustainable
that the catalytic photo-oxidation with oxygen of chemistry is to design and develop alternative products
cyclohexane to cyclohexanol/one, important to those currently adopted. They must be safer and
intermediates of nylon, in the presence of catalysts environmentally more benign, and produced with
such as titanium dioxide, polyoxotungstates or ‘cleaner’ processes which exploit the concepts
metallo-porphyrins, takes place at room temperature examined above. This objective is as complex as it is
and atmospheric pressure. The use of visible light is an obvious, and involves aspects which go far beyond
alternative to Friedel-Crafts acylation, and eliminates strictly chemical concepts, enveloping the whole
the use of Lewis acids such as AlCl3: multi-faceted problem of product design: from aspects
relating to environmental impact and safety of the
O OH O material to energy consumption; to performance
CHO efficiency and the relationship between technical
hn

innovation and change in the production chain, and
O
between technical innovation and change in user
OH
models. The ambitious aim of designing new products
In recent years, considerable interest has developed means the prospect of redesigning of an entire
for alternative activation techniques such as those industrial system.
using microwaves (generally 2.45 GHz) and Three main, partly correlated, lines can be
ultrasounds (20 kHz-1 MHz) – techniques which can distinguished to define new alternative products. The
still be considered as being cutting-edge, but whose first relates to products characterized by a lower
actual industrial application is debatable. In many toxicity and risk, without sacrificing their functional
cases, the use of microwaves allows a marked efficacy. The second aspect consists of new products
reduction in the reaction times by 2-3 orders of deriving from renewable sources, normally of a
magnitude, and is well suited to reactions carried out vegetable origin. The third line is most directly linked
without solvents (for example, by mixing the reagents to applicative aspects, and relates to the development
in the solid state, in water or in neoteric solvents such of products with improved performances and which
as ionic liquids which, due to their high dielectric can be used in a lower quantity, have a longer duration,
constant, are very sensitive to microwaves). As a result require less maintenance, or can be totally or partly
of their characteristics, microwaves are proving to be recycled, with obvious advantages from the
extremely congenial for use in rapid screening, and for environmental impact point of view.
the definition of synthesis protocols in parallel and
combinatorial syntheses for the construction of Less toxic products
databases – in particular, through an impressive series A primary objective for sustainable chemistry is to
of syntheses carried out in the solid state without direct production towards products which are less
solvents with reagents and catalysts supported on toxic, less dangerous and which have a lower impact
substrates, such as alumina, silica or polystyrene (PS; on the environment, while guaranteeing the same
Varma, 2001). functional performances of the products to be possibly
The use of ultrasounds gives rise, in relation to the substituted. The need to move towards less toxic and
power applied, to chemical and physical effects linked environmentally harmless products is a tendency
to acoustic cavitation phenomena, inside and around which has been consolidated for several decades, with
the bubbles which are formed. Under sonication numerous examples also of considerable mass media
conditions, homolithic fragmentations to radical importance, as in the case of prohibiting the use of
species (sonolysis) can be observed, together with chlorinated pesticides (above all DDT), PCBs
excited states and alteration of the solvation, as well as (polychlorobiphenyls) and chlorofluorocarbons. All

these are examples in which widely-used substances are harmless to other organisms), and are capable of
have been banned only after recognition of the degrading to harmless end-products. Within the broad
unpredicted disastrous environmental effects which picture, there is the recent example of spinosad
they have been proved to cause. The objective is much (spinosyn A/D). This is a natural insecticide with a
more ambitious and concerns the ability to direct chemical macro-cyclic lactone structure produced by
research towards the design and development of fermentation, active against mosquito larvae with a
comparatively benign products. The challenge is to high selectivity and general low toxicity, and a
reduce the negative effects of a molecule without favourable environmental profile (Sparks et al., 2001).
sacrificing its functional efficacy. In reality, in many Surprising examples of opportunities provided by
cases, it has been observed that the part of the using alternative products can be found in the field of
molecule that provides the desired activity is separated biocides. Even today, the most widely-used wood
from the part responsible for toxicity or dangerous preservative consists of a mixture of copper,
properties; it is therefore possible to obtain a reduction chromium and arsenic compounds (CCA, Chromated
in risk maintaining the same performances by suitably Copper Arsenate). Only recently have alternative
modifying the molecular structure within the same products been introduced, such as a formulation based
group of compounds. More generally, based on an on a complex of bivalent copper and a quaternary
analysis of the function to be performed, a similar ammonium compound dissolved in ammonia or
result could be obtained using completely different ethanolamine, which eliminate problems induced by
compounds, and without the risks which accompany the presence of arsenic and hexavalent chromium
traditional products. Different strategies can therefore (Award [...], 2002).
be used to design safer products, and the choice In reality, the problem of eliminating toxic and
essentially depends on the amount of information polluting heavy metals from consumer goods is rather
available on the action mechanism, activity-structure generalized and transversal to various product sectors,
correlations, and so forth. When it is difficult to such as paints and varnishes. Pigments based on
intrinsically reduce the molecular hazard, use of the chromium, lead and cadmium, such as lead molybdate,
product can be made less dangerous by reducing its lead chromate and cadmium sulphoselenide, are
bioavailability. In a biological context, for example, traditionally used for covering the range of colours red,
the hydrophilic and lipophilic characteristics or the orange and yellow. They can be validly substituted,
molecular volume can be modified, which often also from an economic point of view, with low toxicity
control the capacity of a substance to pass through azoic dyes that contain harmless alkaline-earth metals
biological membranes. In the environmental field, a such as calcium, strontium and barium, which can also
modification of the lifetime or physico-chemical be used safely in contact with food and drinks, and in
properties of a product can prevent it from reaching or household products (Ritter, 2004). Similarly, yttrium, a
remaining for a sufficient time in areas where it can more common and less toxic element, can replace lead
exert its harmful effects, e.g. the stratosphere for as primer in the cathodic electrodeposition technology
substances with a high ozone reduction potential (electro-coating) used for painting motor vehicles to
(Anastas and Williamson, 1996). protect metal sheets from corrosion (Cahn, 2002).
The fundamental objective of combining low risk
and toxicity with adequate performances is also at the Alternative products from renewable sources
basis of ideas previously expounded concerning The development of new alternative products that
reagents, auxiliaries and solvents used in industrial derive from renewable sources is probably the true
processes. As far as end-products destined for core of the ‘green revolution’ in chemistry (Stevens
consumer use are concerned, this objective has mainly and Verhé, 2004). The utilization of renewable sources
been pursued in specific industrial sectors, such as the is an aspect which has already been dealt with above,
pharmaceutical field and in the production of from another viewpoint, in relation to alternative raw
pesticides. However, its validity is entirely general, as materials. In addition to already consolidated products
it is also followed for obtaining other large-consumer of the current industrial scenario, completely new
products, such as paints and varnishes. products can also be ambitiously obtained from these
In the field of pesticides, for example, there is a raw materials which, apart from their derivation from
gradual shift from: the use of inorganic products renewable sources, have other benign characteristics.
containing arsenic, copper, lead or sulphur; chlorinated The production of these new products often, but not
organic products which are long-lasting in the always, takes place through biotechnological and
environment; towards naturally occurring or bio- biocatalytic processes.
mimetic molecules, such as pyrethroids and A well-known and important example is biodiesel,
pheromones. The latter act on target organisms (but an alternative fuel for diesel engines, consisting of a

SUSTAINABILITY
mixture of methyl esters of fatty acids produced by orgin (chitosan, glycogen) are predictably widely used
methanolysis of triglycerides such as soybean oil, in the medical-pharmaceutical and cosmetic field, but
rapeseed oil, palm oil or exhausted food oils (Knothe also in a wide variety of other industrial sectors
et al., 2004). Biodiesel improves the lubricating power (Lapasin and Pricl, 1995).
of the fuel and, like most oxygenated fuels, Polylactic acid (PLA) and polyaspartate (TPA) are
is capable of reducing emissions deriving from polymers produced from renewable raw materials that
combustion. Esters of fatty acids are also used as have been recently introduced. Lactic acid is obtained
lubricants, cut oils and solvents. from the fermentation of sugars contained in maize
The fact is that nowadays, there are a large number flour and, after distillation, is transformed first into
of proposals for the upgrading of renewable raw lactide and then into the high molecular weight
materials to functional new generation materials. polymer. Polylactic acid is biodegradable or can be
Among the foremost of these are polymers (Gross and recycled (lactic acid is re-obtained by hydrolysis), and
Kalra, 2002): this marks a come-back given that, is used in the field of textile fibres and packaging
before the era of low-priced petroleum and the (Vink et al., 2003). Polyaspartate is a new
introduction of synthetic polymers, polymers deriving hydrosoluble and biodegradable biopolymer
from renewable sources were already widely used. The synthesized from L-aspartic acid, a naturally occurring
production of bio-plastics based on starch, a product amino acid. Polyaspartate is used as an alternative to
abundantly available in maize and other plants, is polyacrylates, which are not biodegradable, as a
continuously increasing on the market. These corrosion and scale inhibitor for water treatment, and
bio-plastics are especially used in specific applications as an anti-scale dispersing agent in detergents (Cann
which require biodegradability as a functional and Connelly, 2000).
characteristic: compostable bags for recycling food It is interesting to note that in an important product
waste, disposable tableware, packaging materials, sector, i.e. surface-active agents for detergents, the
products for personal hygiene, agriculture and hydrophobic fraction of the surface-active molecule
farming. However, applications with a greater prevalently derives from renewable sources (palm oil
technological content are also emerging, such as the or coconut oil), also in traditional industrial lines.
use of bio-plastics in tyres for motor vehicles (Bastioli, Surface-active agents have recently been developed in
2002). As a result of their good biocompatibility, which the hydrophilic part also derives from renewable
biodegradability and atoxicity properties, sources, substituting ethoxylated derivatives produced
polysaccharides of a vegetable origin (cellulose, from ethylene oxide, with derivatives of sugars such as
pectin, gum Arabic), of a marine (alginates, agar), saccharose, glucose or sorbitol (von Rybinski and Hill,
microbial (dextran, xanthan, scleroglucane) or animal 1998). Both non ionic and anionic surface-active
agents can therefore be obtained by suitably
functionalizing the structure of the carbohydrate.
BIO Products with an improved performance

POLYMERS Among materials provided by the chemical
industry, mention must be made of the predominant
and growing importance of polymers in applications
which, from case to case, can have a long life (as in
PE/PP constructions), a medium duration (such as motor
vehicles), or short life (packagings). Excluding aspects
relating to production processes, which are also
PS extremely important, all improvements in the
mechanical and applicative characteristics, duration,
recyclability, easy disposal of products based on
PET polymeric materials, have enormous repercussions on
the ecosystem. The increasing capacity to control the
molecular structure of polymers and new production
ABS
technologies enable a continuous expansion of the
PU types of polymers produced to satisfy market demands
PVC as specifically and precisely as possible, thus
guaranteeing the production of better products
(Romano and Garbassi, 2000): for example, new
Fig. 9. Polymers and sustainability. grades of high density polyethylene (HDPE), the most

widely-used polymer, characterized by a bimodal of fossil fuels and controversial issues, following the
molecular weight distribution, allow a decrease of accelerated alteration observed in the composition of
33% in the thickness of polyethylene tubes, with a the atmosphere. Finally, the recent impressive
corresponding saving of material. The greater technical and scientific developments of
versatility of the typologies available often favours the biotechnology – from new enzymes to biocatalysis,
substitution of environmentally more problematic from genomics to metabolic engineering – open up
materials: this is the case, for example, of the completely new prospects for the use of raw materials
substitution in primis of polyvinylchloride (PVC) and from renewable sources.
polyurethanes (PU; Fig. 9).
Polyolefins (PE, polyethylene; PP, polypropylene) Biorefinery
have the great advantage of consisting of carbon and The concept of biorefinery emerges within the
hydrogen alone, and of being free of aromatic context of this expected future growth in the use of
components. As a result of their physico-chemical and materials from renewable sources (Realff and Abbas,
applicative characteristics, as well as their production 2004). The development of the concept of biorefinery
technologies, they are considered as being among the is associated with the idea that producing chemical
most environmentally compatible plastic materials. products and materials from biological sources to
Linear low density polyethylenes (LLDPE), for substitute petrochemical ones must make use of
example, produced with metallocene catalysts, are similar concepts to those which led to the affirmation
eroding the polyurethane and PVC market in the field of traditional refineries producing from crude oil, but
of motor vehicles and carpet underlay: in this latter with inevitable essential differences.
application, unlike before, this allows an easy total The possibility of completely replacing petroleum
recycling of both the lower plastic layer and also the as a main energy source with biomasses is obviously
upper layer made of nylon fibre, as the polyolefin is not disputed: the consumption of crude oil for
compatible with the de-polymerization of nylon to petrochemical production does not exceed 3% of the
caprolactam monomer for subsequent reuse (Segars total consumption, and the replacement of fossil fuel
et al., 2003). Polypropylene reinforced with glass fibre as energy source cannot but envisage resort to other
is capable of competing, from the performance point alternative forms of energy.
of view, with PET and nylon. The field of reinforced An important aspect of the traditional chemical
polymers is fully evolving: the use of nanocomposites industry is that careful planning, and optimum
is reported to be revolutionary, and envisages an even management of materials and energy are vital for its
fiercer competition between the various polymers and success, and that the transformation of the greatest
materials. possible amount of raw material into high-quality
products is at the basis of new process technologies. The
essential characteristic of oil refineries is that they
9.6.4 Looking ahead handle complex mixtures. In addition to useful
molecules, these mixtures contain ones that seem
It has been widely demonstrated how renewable useless and undesirable at first sight, but are upgraded
sources represent an essential component of (through suitable processes set up during technological
sustainable development. Producing chemical products development) to produce useful products for the market.
from renewable sources is not in itself a new idea: up Biorefinery follows the same model, accompanied by
until the first part of the Twentieth century, in fact, various specific aspects. Biological (agricultural) raw
most chemical products derived from these. materials are also complex materials with components
Subsequently, due to the overwhelming development which cannot be used immediately. It will be up to
of the oil industry during the century, the situation biorefineries to find a way to make the best possible use
changed and, today, only about 5% of chemical of most of these renewable raw materials.
products derives from biological renewable sources. Operations for the utilization of petroleum and
This situation seems destined to change again for biomasses have surprisingly similar aspects from a
various reasons (Wedin, 2004). The first relates to conceptual point of view. They comprise: stabilization
doubts as to the amount and availability of oil reserves and transportation, separation (for example,
still exploitable with consequent repercussions on the distillation), purification, decomposition (e.g.
prices, also in view of the increases in consumption by cracking), transformation (such as reforming). To
the developing countries: various predictions estimate carry out these operations, an oil refinery substantially
the peak of overall oil production as being between relies on chemical or physico-chemical principles,
2005 and 2010. The second reason concerns the whereas a biorefinery must also resort to agricultural
production of carbon dioxide connected with the use and biological techniques.

SUSTAINABILITY
Alongside these similar aspects, there are also the production of industrial end-products. The process
differences. One of the characteristics of fossil fuel is operations can be of a biological nature or chemical
that it is highly localized and can be easily transported, fermentation, combined with extraction,
because it has a high utilization density. This allows thermo-chemical and hydrolysis processes. The
the formation of relatively few transformation knots, development of biorefineries must have the
with consequent significant scale economies in the cooperation of enterprises operating in the agricultural
process phase. The inherent environmental problems field and chemical sector with the participation of
are therefore concentrated around the area in question. partners who possess the know-how relating to
Masses of a biological origin, on the other contrary, innovative biotechnologies.
are normally much more widespread over the territory The development of more efficient and cheaper
and long-distance transportation is often costly, also in processes for the pretreatment and separation of the
relation to the low apparent densities and high water main components of biomasses is the first essential
content. Furthermore, the differentiation already step for an effective development of biorefineries.
existing in the plant (leaves, seeds, ligneous part, etc.) These processes (on which a concerted effort is being
allows an initial separation which exploits mechanical made) must utilize a heterogeneity of fibrous
energy, rather than having to resort to a phase lignocellulose materials and other waste by-products
separation or separation at a molecular level which from herbaceous, arboreal or forest crops such as
exploits thermo-chemical energy as in the case of molasses, shells, stems, straw, brushwood, etc.; these
petroleum. This opens up the prospect of a widespread derive, for example, from processing maize, sugar
relocation of transformation plants, at least as far as a beet, soya, and are widely available at a very low cost.
first pretreatment phase is concerned, allowing There are two main types of biomasses, those
cheaper and easier transportation. This seems consisting of starches and those of lignocellulose
reasonable also because of the fewer environmental products. Both contain polymers of sugars which must
problems involved: possible waste materials can be be reduced to their monomeric components before
easily biodegraded and a simple disposal procedure is being subjected to chemical or fermentative
represented by their reuse as soil nutrients to help transformation processes. Whereas the reduction of
guarantee the renewal of sources in loco. Scale starches to glucose is relatively easy, the treatment of
economies suggest an intermediate concentration of cellulose to give sugars is much more difficult due to
biomass in liquid form for conveyance to a its crystallinity, resistance to hydrolysis and its close
central biorefinery. The widespread relocation of association with hemi-cellulose and lignin through
transformation plants has evident social implications. covalent bonds.
Once the biomass is conveniently concentrated for There are likely to be extremely promising
subsequent transformations, it must be restored to a developments as a result of steam explosion treatment,
limited number of intermediates (building blocks) for which one of the most important pilot plants exists
from which consumer materials can be produced. The in Italy (Zimbardi et al., 2002). This process subjects
stronghold of an oil refinery is the distillation column lignocellulose material to the action of saturated water
which separates the hydrocarbons present in crude oil, vapour at a high pressure (15-30 bar) and temperature
substantially containing carbon and hydrogen, on the (180-230°C) for a short period of time (1-10 min),
basis of the number of carbon atoms, from 3 to about followed by rapid depressurization to atmospheric
20-30. Other physical and chemical operations, such pressure which causes an explosive decompression
as extraction, cracking, etc., allow production to be with a fibre disruption of the biomass. The treatment
focused on obtaining the intermediates most in allows an effective separation of the three different
demand for the production of the desired products and fractions that form the vegetable biomass (hemi-
materials (fuels, solvents, ethylene, propylene, cellulose, cellulose and lignin). Other degradation
aromatic compounds, etc.). In biorefineries, the range strategies of lignocellulose materials are acid
of carbon atom numbers is very different, and varies hydrolysis and supercritical extraction. The cellulose,
from a significant fraction centred between 5 to 7 thus separated and purified, can be more easily
carbon atoms (simple sugars) to an intermediate transformed into sugars through the action of suitable
fraction based on oligomeric sugars, up to molecules micro-organisms capable of producing enzymes
containing hundreds of carbon atoms in the fraction (cellulase) which hydrolyse and break up the cellulose.
defined as lignocellulose (hemi-celluloses, cellulose Purified lignin can also, in turn, form the raw material
and lignin). Biomasses, moreover, contain a large for producing a variety of chemical products through
quantity of oxygen and alkaline metals in their more traditional chemical treatment.
molecules. These different characteristics modify and Once the sugar step has been reached, the next step
partially complicate the synthetic pathways towards involves converting the sugars to the desired products,

ranging from pharmaceutical products to industrial These transformation pathways of biorefineries

intermediates, polymers, and solvents up to the envisage a wide use of biocatalysis through the
production of fuels (Lichtenthaler and Peters, 2004). exploitation of recent progress in biotechnology
As in traditional refineries, biorefineries must be able (Webster et al., 1996). The term biocatalysis refers to a
not only to use all the raw material available, but also chemical reaction which is catalysed either by an
transform it into the multitude of products, with an entire living organism (such as a microbe) or by a
extremely diversified and wide range of utilization and specific enzyme deriving from an organism. Through
added value, which is now a prerogative in the oil metabolic engineering techniques (recombinant DNA
industry. The oil industry begins with the refinery technique), it is possible to modify part of the normal
which produces fuels and extends as far as fine and metabolism of a cell to gear it towards producing the
specialty chemicals and pharmaceuticals. Similarly, desired product. There are numerous examples, at
biorefineries will also have to take on the present mostly limited in practice to specialty
responsibility of the most varied productions. Ethanol, chemistry, but with the prospect of being applied to
for example, which is produced through the traditional commodities production, of products obtained using
fermentation of glucose or through more Escherichia coli or other suitably modified micro-
innovative fermentative processes using sugars that organisms. Some examples have already been
derive from lignocellulose, is an excellent alternative provided above, relating to the utilization of raw
fuel already widely used for motor vehicles. materials from renewable sources.
Fundamental intermediates such as acetic acid, lactic The future holds new exciting possibilities, such
acid and succinic acid can also be obtained by as the use of extremophilic enzymes, catalytic
fermentation. Acetic acid is now already one of the antibodies and ribozymes. Extremophilic enzymes
most important industrial intermediates. Lactic acid is are capable of acting under extreme conditions such
a basis for the production of new solvents (ethyl as high temperature, high saline concentration,
lactate) and biopolymers (the above-mentioned PLA, supercritical conditions, and organic solvents.
polylactic acid). Succinic acid is also a starting point Catalytic antibodies are obtained by injecting a
for numerous useful products, such as solvents and hapten (i.e. a small molecule capable of generating
intermediates for polymers. an immunitary response when it is attached to a
Three strategies can be basically identified for protein) into an animal, which is analogous to the
substituting products deriving from petroleum with transition state of the desired reaction. Catalytic
products deriving from biomasses: direct substitution antibodies have similar catalytic properties to
of the petroleum-derived product with the same enzymes, but they can be generated and isolated
product deriving from biomass (for example, ethanol, within a few weeks. An ambitious objective is the
ethylene, acetic acid); indirect substitution with a development of antibodies capable of catalysing new
product functionally similar but chemically different; chemical reactions, unknown to their naturally
substitution with an intrinsically new product, for occurring enzymatic counterparts. Finally,
example, substitution of a synthetic polymer with a ribozymes are ribonucleic acids which, once suitably
degradable biopolymer. manipulated, have proved to be capable of exerting
Fig. 10. Biorefinery.

SUGARS
biochemical platform
FUELS
BIOMASS HEAT CHEMICALS
POWER MATERIALS
SYNGAS
thermochemical platform

SUSTAINABILITY
functions typical of protein enzymes in the specific waste products and by-products of one industry are
catalysis of reactions. compensated by the raw materials required by another
An effective scale-up of biochemical processes is a industry, and the sum of the integrated processes does
further obstacle to be overcome before biorefineries not produce any waste. The exhaustive use of
take hold. Many fermentative processes, for example, raw materials, combined with a shift towards raw
give rise to diluted aqueous solutions from which the materials deriving from renewable sources, aims to
desired products can be recovered. This requires take the utilization of world resources back towards
separation and purification technologies which are sustainable levels. In a biorefinery integrated cluster,
different from the more consolidated technologies of thanks to photosynthesis, the production and
the petrochemical industry, such as the use of utilization of carbon dioxide, also represent a closed
membranes, liquid-liquid extraction techniques or cycle. This is one of the main advantages of
electrodialysis techniques. The problem of the product biorefineries compared to the use of raw materials of
inhibiting the reaction, which causes the low a fossil origin.
concentration of the final products, can be overcome The concept of a zero emissions industrial system
by developing continuous removal techniques of the increases the ecoefficiency not only by completely
product itself, similar to what is done in reactions eliminating waste- and by-products, but at the same
characterized by unfavourable thermodynamic time maximizing the productivity of resources. It
equilibrium. intends to represent a third historical phase of the
The biorefinery concept is based on the use of control and reduction of emissions, following the first
sugars (but also phenol derivatives of lignin and phase which manages pollution issues once they have
triglycerides, for example biodiesel) deriving from occurred, and the second phase which applies
biomasses, which uses largely biochemical conversion preventive strategies for the reduction of emissions
processes. Alongside this is a perhaps less innovative and environmental risks.
biorefinery concept based on thermo-chemical
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9.

9.6.1 Sustainability inextricably linked to the concept of development

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 879

880 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 881

882 ENCYCLOPAEDIA OF HYDROCARBONS

Table 1. Measurement parameters of the sustainability of a chemical process

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 883

INDUSTRIAL SEGMENT Product quantity (t/yr) kgwaste/kgproduct

Petrochemicals and refining 106-108 0.1

884 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 885

controlled and targeted reactivity

886 ENCYCLOPAEDIA OF HYDROCARBONS

not vice versa, by suitably modulating the Alternative raw materials

b) alternative synthesis methods or alternative

reagents; c) alternative reaction conditions;

new synthesis method primarily aimed at improving

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 887

gas partial Fischer-

Fig. 2. Use of natural gas as alternative raw material.

888 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 889

recycle (asphaltenescatalyst) purge

gas oil from HDS desulphurized gas oil

refinery peroxidation oxidation separation

Fig. 4. ULSD process.

890 ENCYCLOPAEDIA OF HYDROCARBONS

utilization of CO2 already in the context of large

In the presence of a different catalytic system, the Replacement of hazardous reagents

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 891

product to CO generation unit

892 ENCYCLOPAEDIA OF HYDROCARBONS

Fig. 6. Production of aromatic polycarbonates without the use of phosgene:

synthesis of the carbonate used as reagent. For Replacement of stoichiometric reagents

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 893

894 ENCYCLOPAEDIA OF HYDROCARBONS

OH OH OH Similar problems, relating to marketing the acetone

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 895

896 ENCYCLOPAEDIA OF HYDROCARBONS

As already mentioned, this avoids the use of a NO2

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 897

The new reaction completely avoids the AlCl3 NaOC2H5

898 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 899

900 ENCYCLOPAEDIA OF HYDROCARBONS

Fig. 7. Ionic liquids.

O generally a salt of a quaternary ammonium or

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 901

Fig. 8. Difasol process.

902 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 903

904 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 905

BIO Products with an improved performance

906 ENCYCLOPAEDIA OF HYDROCARBONS

VOLUME III / NEW DEVELOPMENTS: ENERGY, TRANSPORT, SUSTAINABILITY 907

908 ENCYCLOPAEDIA OF HYDROCARBONS

ranging from pharmaceutical products to industrial These transformation pathways of biorefineries

Fig. 10. Biorefinery.

recycle (asphaltenescatalyst) purge