Sie sind auf Seite 1von 9

View Article Online / Journal Homepage / Table of Contents for this issue

Green Chemistry Dynamic Article Links

Cite this: Green Chem., 2011, 13, 367 PAPER
Comparative cradle-to-gate life cycle assessments of cellulose dissolution
with 1-butyl-3-methylimidazolium chloride and
Serena Righi,*a Andrea Morfino,a Paola Galletti,a Chiara Samorı̀,a Alessandro Tugnolib and
Carlo Stramigiolib
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

Received 4th October 2010, Accepted 25th November 2010

DOI: 10.1039/c0gc00647e

In this paper the expected environmental impacts of the industrial cellulose dissolution with the
ionic liquid 1-butyl-3-methylimidazolium chloride (Bmim Cl) were analyzed through a “cradle to
gate” Life Cycle Assessment (LCA). In order to weigh up the “greenness” of the process, the
analysis was performed through a comparison with the well established environmental friendly
N-methyl-morpholine-N-oxide (NMMO)/H2 O process. Although dissolution of cellulose in
Bmim Cl has not been used for industrial production of cellulose fibers to date, results from LCA
suggest that it could be interesting from an environmental point of view since its impacts are
similar to those of the NMMO/H2 O process. Specifically, the process with Bmim Cl generates a
higher environmental load on abiotic resource depletion, emissions of volatile organic compounds
and ecotoxicity than the NMMO/H2 O process. Conversely it has some environmental advantages
with regards to human toxicity. In both cellulose dissolution processes, the major contributions to
the environmental impacts come from precursor syntheses. In addition to the comparative analysis
of the two cellulose dissolution processes, the paper reports the complete life cycle inventory (LCI)
of the two solvents, Bmim Cl and NMMO, and their life cycle impact assessment (LCIA).

Introduction For example, the viscose Rayon process is a worldwide technol-

ogy based on the conversion of cellulose into sodium cellulose
Cellulose is the most abundant renewable resource in the world,
xanthate, soluble in a caustic solution, making it possible to
and its use as an unmodified material, e.g. cotton, or as a deriva-
wet-spin the polymer into a fibre or film, but, at the same time,
tive, through chemical, enzymatic or microbiological modifica-
this process is accompanied by environmentally hazardous by-
tion processes, is largely widespread. Cellulose has very strong
products, namely H2 S, CS2 and heavy metals.
intermolecular bonds, which prevent the melting of the material
In recent years new cellulose dissolution methods have been
and the dissolution in the major part of traditional available
researched quite extensively, looking for new environmentally
solvents. For this reason cellulose and lignocellulosic biomasses
friendly solvents suitable for the process. Among the new
in general have been isolated and treated with technologies
non-viscose processes currently in use in the industry for
which cannot be considered as environmental friendly (e.g.
manufacturing regenerated cellulose fibres and films, the N-
harsh alkaline or acidic conditions are involved, the few suitable
methyl-morpholine-N-oxide (NMMO)/H2 O process (called the
organic solvents lack greenness since they are often highly
Lyocell process) appears to be the most promising replacement
volatile, toxic, instable, costly, not recyclable, and give difficulty
for conventional viscose Rayon process.1
in the modification of the properties of the polymer itself).1
The feature of the NMMO/H2 O process is a closed water
This means that traditional cellulose dissolution processes,
circuit with an extremely high recovery rate of the solvent (99%),
including the cuprammonium and xanthate processes (Rayon
a short production cycle (the dissolution and spinning process
process), are often cumbersome, expensive and non-sustainable.
is usually done within 5 h) and the possibility to operate with
highly concentrated cellulose solutions (25–35%). Additionally,
Centro Interdipartimentale di Ricerca per le Scienze Ambientali it is more environmentally-friendly than the viscose Rayon
(CIRSA), Alma Mater Studiorum - University of Bologna, via processes,2 because it does not produce toxic gases or by-
S.Alberto 163, 48123, Ravenna, Italy products and the solvent itself is biodegradable and nontoxic.3,4
Dipartimento di Ingegneria Chimica, Mineraria e delle Tecnologie
Ambientali (DICMA), Alma Mater Studiorum - University of Bologna,
However it is important to recognize that Lyocell process also
via Terracini 28, 40131, Bologna, Italy involves some drawbacks, such as high operation temperatures,

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 367–375 | 367
View Article Online

partial cellulose degradation and temporary or permanent over its entire life cycle. A complete LCA study addresses
discoloration of the resulting fibres, side reactions, pronounced the environmental aspects and potential environmental impacts
decomposition of NMMO, increased consumption of stabilizers throughout a product life cycle, from raw material acquisition
and high costs.5 For this reason the investigation on new solvents through production, use, end-of-life treatment, recycling and
able to overcome these disadvantages and, at the same time, to final disposal (i.e. cradle-to-grave).22 However, LCA studies can
efficiently dissolve cellulose is still very important. also include only selected life cycle stages, e.g. from raw materials
Ionic liquids (ILs) are a class of organic salts with relatively extraction to product manufacture; in this case it is referred to
low melting points (below 100 ◦ C) and unique combinations as cradle-to-gate analysis, which is the approach utilized in the
of properties dependent on the combination of cations and current study.
anions which can be independently modified.6–8 So far, they According to ISO 14040 guidelines,23 the LCA methodology
have been used to replace the organic solvents in a large number comprises four steps: goal and scope definition, inventory
of applications, taking advantage of unique properties such as analysis, impact assessment, interpretation. Goal and scope
the capability to dissolve hardly soluble materials, the lack of definition is the step in which the study objectives, the function
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

vapour pressure, the chemical and thermal stability and the ease of the product, the functional unit and the boundaries of the
of recovery and recycle.9–12 system are defined. Life cycle inventory analysis (LCI) is the step
Some recent studies on a laboratory scale have demonstrated of an LCA in which the material and energy flows are compiled
the use of ionic liquids as alternative “clean” technology and quantified. The third phase, Life cycle impact assessment
in biomass applications, in particular in the dissolution and (LCIA), is based on the aggregation of the environmental
derivatisation processes of cellulose and wood;13–20 the most impacts quantified in the inventory analysis into a limited set of
important results have been obtained with hydrophilic ionic recognizable impact categories (e.g. global warming potential)
liquids based on the cation 1-alkyl-3-methylimidazolium, ion and corresponding indicators (e.g. kg CO2 equivalents). The
paired with coordinating anions such as chlorides, phosphates last step, Interpretation, is a systematic procedure to evaluate
or acetates.17,21 1-Butyl-3-methylimidazolium chloride (Bmim the information from the inventory analysis and the impact
Cl) is the most studied ionic liquid in biomass dissolution assessment of the product system and to draw conclusions from
processes because of the ability of chloride anions to break all of the foregoing results of the study.
the hydrogen bonding network present in cellulose; moreover, In the present study the LCA software Gabi 4 by PE
by exploiting the immiscibility properties of cellulose and the International24 was employed to support the life cycle inventory
high hydrophilicity of Bmim Cl, the polymer can be precipitated and analysis of the two cellulose dissolution processes.
by simply adding water (or organic precipitation solutions) to
the mixture. The regenerated cellulose obtained in this way has Goal and scope definition. The major goal of this study
a similar degree of polymerization and polydispersion of the was to develop the “cradle-to-gate” life cycle inventory of both
cellulose in the original material. The dissolution of cellulose in Bmim Cl and NMMO/H2 O cellulose dissolution processes and
Bmim Cl ranges from 3% to 25% (wt%) according to the degree to analyse and compare the environmental impacts of the two
of polymerization of the biopolymer and to the source of energy envisaged industrial processes.
applied (ultrasounds, microwaves irradiation and heating);13,15 The analyzed systems were: i) the cellulose dissolution process
the best results have been obtained under microwaves impulses with NMMO/H2 O, ii) the dissolution process with Bmim Cl
(25% wt) probably because the adsorption of microwaves by and iii) all the upstream processes in production chain. Since
polar solvents, such as ionic liquids, is very strong and warming the main purpose of the system was to dissolve cellulose
occurs quickly.13 pulp to obtain textile fibres, the chosen LCA functional unit
This article aims to compare the expected environmental (i.e. reference unit of production) was 1 kg of the dissolved
impacts of the two cellulose dissolution methods, if applied at cellulose.
industrial production level: the well established environmentally The system boundaries (Fig. 1) included all upstream pro-
friendly non-viscose processes with NMMO/H2 O and the cesses, as cellulose pulp production, energy and chemicals
candidate process with Bmim Cl. The energy and environmental production, and transportations, necessary to operate the pulp
loads expected from each process were estimated by using a dissolution process. These boundaries have been chosen since
chemical process simulation software. The results constituted downstream contributions are expected to be independent of
the input for the application of the Life Cycle Assessment (LCA) the dissolution process used.
methodology. In addition, the complete life cycle inventory For both the assessed systems, the following assumptions have
(LCI) of the two solvents, Bmim Cl and NMMO, and their been made:
life cycle impact assessment (LCIA) were quantified, and the ∑ For database consistency issues, all the industrial processes
most significant environmental input and output flows were analysed in this paper were located in Germany. For import of
identified (i.e. the hot spots, to provide a foundation for future resources (e.g. natural gas), the boundaries were extended: the
improvement and optimisation of the processes). available data was partly based on global, European or Swiss
average values. Cellulose pulp production process was from
Eucalyptus ssp. and has been located in Thailand.25
Life cycle assessment
∑ According to Frischknecht et al.26 and to Hischier et al.,27
LCA is the most extensively developed and standardized standard distances were assumed for transport of goods. With
methodology for identifying and assessing the potential envi- regard to basic chemicals we estimated these standard distances
ronmental impacts associated with a product, process or service to be 100 km lorry and 600 km train transport within Europe.

368 | Green Chem., 2011, 13, 367–375 This journal is © The Royal Society of Chemistry 2011
View Article Online

recent years, CPS has advanced to the point that detailed models
can replace expensive pilot-scale projects.32 There are several
CPS software packages commonly used; here Aspen Plus R
has been adopted.33 The simulations were carried out for the
syntheses of: Bmim Cl, NMMO and all precursors whose data
were not already included in LCA database.
The typical inputs of a CPS involve the definition of the
chemical components, the selection of thermodynamic and
property models, the definition of a process flow diagram
(scheme of operations and units) and the specification of
input flows and operating conditions (flow rate, composition,
temperature, pressure, etc.). The properties of most of the
common chemicals were available in the simulator database and
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

were utilized. In cases in which the information was not available,

the required physical properties were obtained from relevant
technical literature. The process flow diagrams (PFD) were
designed by selecting and connecting the unit operations relevant
for the industrial process of interest (e.g. reactors, separators,
distillation columns, heat exchangers, etc.). The solution by
the CPS of the energy and material balances as well as the
preliminary sizing of major units allowed for the estimation of
the overall process conversions, the energy consumption (both
thermal and electric) and the waste stream production. These
data were the essential input for the definition of the process
LCI by Gabi 4.
Impact assessment. In current study, classification and
Fig. 1 System boundaries.
characterisation stages have been considered in the impact
∑ According to Hischier et al.,27 emissions to air were assessment phase in LCA methodology,23 only. Normalization
estimated on the assumption that 0.2% of the input materials and evaluation were excluded since they are considered optional
were emitted to air. The water emissions were calculated as the by ISO 14044 and, according to the goal and scope defined here,
difference between the unreacted input materials and the air they would not provide extra useful information.
emissions. In the calculation of impact indicators, the LCA methodology
∑ As the importance of the infrastructure of a chemical pro- based on CML 2001 developed by the University of Leiden
duction plant is commonly assumed to be low27 or insignificant,28 have been used.34 The environmental impact categories here
in this study the impacts from construction and maintenance of considered have been: abiotic resources depletion potential
production plant and equipment were neglected. (ADP), global warming potential (GWP), ozone depletion
potential (ODP), human toxicity potential (HTP), acidification
Inventory analysis. Background data for: i) production of potential (AP), eutrophication potential (EP), photochemical
electricity, steam, and fossil fuel; ii) transport system and iii) ozone creation potential (POCP), freshwater aquatic ecotoxicity
available chemical processes were taken from Gabi 4 database. potential (FAETP) and terrestrial ecotoxicity potential (TETP).
LCA databases do not include all the required chemical pro- Moreover, emission of volatile organic compounds (VOCs) has
cesses; so the major part of the processes were reconstructed been considered, since a low emission of these compounds
through the support of a Chemical Process Simulation (CPS) is usually considered as an important issue in favour of the
software that permits the completion of material and energy “greenness” of ILs.
balances, as well as the preliminary sizing of process units (that
defines e.g. the efficiency of separation units). New processes Chemical process description
for which an industrial scale-up has not been developed to date
Bmim Cl synthesis process. Bmim Cl synthesis method
(e.g. Bmim Cl dissolution of cellulose), were inferred from lab-
reported by Park and Kazlauskas35 was adopted as the basis
scale studies on the basis of good engineering practice in design.
to the preliminary design of the industrial scale plant (reference
While it is recognized that the actual scale-up would require
potentiality of the production line 5 ¥ 105 kg/y of Bmim Cl).
extensive research efforts, this simplified approach is adequate in
The proposed process for the production of Bmim Cl was a
the scope of current study, since it yields a preliminary estimation
discontinuous three-step batch process (Fig. 2). In the first step,
of expected material and energy flows.29,30
1-chlorobutane (1.1 eq) was reacted with 1-methylimidazole in
In addition to Gabi 4 database and the CPS software,
a batch reactor at 80 ◦ C for 36 h. In the second step, the excess
also technical literature and reference books were used as
of unreacted 1-chlorobutane was removed by evaporation at
information sources.
130 ◦ C and subsequently condensed, with an overall process
Process simulation. Chemical process simulators are soft- time estimated of approximately 1 h. In the third step, ethyl
ware programs designed to model and size process plants.31 In acetate was added to the batch reactor in order to facilitate

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 367–375 | 369
View Article Online

remove any trace of organic compounds and water. Ethyl acetate

was recovered by condensation and purified by distillation. Since
1-chlorobutane, ethyl acetate, 1-methylimidazolium and its pre-
cursors monomethylamine (CH3 NH2 ) and glyoxal (CHOCHO)
were not included in Gabi 4 database, their production processes
were also simulated by Aspen Plus R (Fig. 3a) according to
relevant patents and technical literature.36–40 Inventory data of
n-butanol were obtained from Buwal database;41 while inventory
data of all remaining chemicals were from Gabi 4 database.

Fig. 2 Process flow diagram considered for Bmim Cl manufacturing NMMO synthesis process. The NMMO synthesis reported
process. by Scholten and Rindtorff42 was used to simulate the in-
dustrial production process by the Aspen Plus R software
crystallisation of the reaction product and remove the residual (reference potentiality of the production line 2.5 ¥ 106 kg/y
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

impurities. The Bmim Cl product was separated by filtration and of NMMO). In the considered process, an azeotropic mixture
subsequently dried at 90 ◦ C by an inert gas stream in order to of N-methylmorpholine (NMM) and water (73.5% of NMM)

Fig. 3 Diagram of the synthesis processes modelled through Aspen Plus

R involved in the Bmim Cl (Fig. 3a) and NMMO/H2 O (Fig. 3b) manufacture
chains. All values are referred to 1 kg of final product.

370 | Green Chem., 2011, 13, 367–375 This journal is © The Royal Society of Chemistry 2011
View Article Online

was oxidized with hydrogen peroxide (35%) at 70 ◦ C for Table 1 Characterization results for 1 kg of Bmim Cl and NMMO
2 h to give NMMO as a 59% solution in water. Residual production
water was distilled and recycled, as well as any recoverable Total score
hydrogen peroxide. Since NMM entry was not included in
Gabi 4 database, its production process was also simulated by Impact category Bmim Cl NMMO Unit
Aspen PlusR (Fig. 3b). The NMM synthesis method described
Abiotic resources depletion (ADP) 6.1E-02 2.9E-02 kg Sb-eq
by Simon et al.43 was adopted as reference. In that process, Global warming potential (GWP) 6.4E+00 3.3E+00 kg CO2 -eq
monomethylamine and diethylene glycol were contacted in a Ozone depletion potential (ODP) 1.3E-07 1.0E-07 kg CFC11-eq
bed of copper and magnesium silicate prepared at 240 ◦ C. After Human toxicity potential (HTP) 1.3E-01 2.2E-01 kg DCB-eq
Acidification potential (AP) 1.6E-02 5.6E-03 kg SO2 -eq
the NMM synthesis, monomethylamine and diethylene glycol Eutrophication potential (EP) 3.8E-03 3.2E-03 kg PO4 3- -eq
were recovered and reused through distillation. Photochemical ozone creation 7.0E-03 8.1E-04 kg C2 H-eq
potential (POCP)
Freshwater aquatic ecotoxicity 1.0E+00 3.3E-02 kg DCB-eq
Cellulose dissolution process potential (FAETP)
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

Terrestrial ecotoxicity potential 8.2E-03 4.6E-03 kg DCB-eq

Cellulose dissolution process with NMMO/H2 O. The cel- (TETP)
lulose dissolution method with NMMO/H2 O developed by Volatile organic compounds 4.0E-02 1.2E-02 kg
McCorsley44 and used as comparison in a study on dissolution (VOCs)
with ionic liquids by Kosan and co-authors45 was adopted. A
cellulose solution was prepared by mixing pulp and solvent (59%
NMMO in water) in a mixer under vacuum. The solution was
then placed in a feed tank and held at 94 ◦ C. Then maintaining
this temperature, the dope was pumped through a filter. The
solution was sent to a gear pump which forced it through a
spinneret having 90–100 mm diameter holes. The dope filaments
were passed through an air gap into a NMMO/H2 O bath, and
from there via appropriate guides to a winder. The resulting
fibre was washed with water and the solvent was recovered. The
reference potentiality of the production line is assumed of 8 ¥
103 kg/y of cellulose fibre.

Cellulose dissolution process with Bmim Cl. Steps, pro-

cess units and potentiality of the cellulose dissolution with
Bmim Cl were taken to be equal to NMMO/H2 O dissolution
process modifying only the molar ratio between cellulose and
solvent (1 : 6 instead of 1 : 8) and the spinning mass temperature
(116 ◦ C instead of 94 ◦ C) as used by Kosan and co-authors
on laboratory-scale.45 These changes have been done in order
to obtain similar mechanic characteristics of the fibre found by
Kosan and co-authors in their approach. Fig. 4 Alternative block diagram of cellulose dissolution (left branch
Since water solubility of the two solvent is very high and both with Bmim Cl and right branch with NMMO/H2 O). MR: molar ratio.
have a boiling point higher than water, the same recovery of the
solvent, i.e. 99%, was assumed.
It is important to note that, all common phases (which would Cl LCA. This conclusion agreed with findings by Kralisch
not affect the comparison) were neglected. and co-authors46 which highlighted high cumulative energy
The block diagram for the alternative processes with Bmim demand (related to GWP) and medium human toxicity of 1-
Cl and with NMMO/H2 O is shown in Fig. 4. methylimidazole and medium ecotoxicity of 1-chlorobutane for
aquatic organisms. Our characterization results were also in
good agreement with those reported by Zhang47 for the ionic
Results and discussion liquid Bmim BF4 obtainable directly from Bmim Cl and NaBF4 ,
confirming the high environmental impact of the production
Inventory and impact analysis of Bmim Cl synthesis
chain leading to the synthesis of these compounds.
The Bmim Cl synthesis process presents a long supply chain Fig. 5 shows the percentage contributions to impact categories
from natural resources to the end product, therefore it requires of main starting materials for the syntheses of Bmim Cl and
large quantities of materials, energy and solvents and it involves NMMO. As regards Bmim Cl, it appears that the major impacts
organic compounds emissions in air and water. The total score in all categories come from 1-methylimidazole synthesis. About
of each environmental impact category (LCIA) resulting from 60% of abiotic resource depletion came from 1-methylimidazole
classification and characterization of Bmim Cl production is and was associated with fossil fuels consumption for en-
shown in Table 1. Global warming, freshwater aquatic ecotox- ergy and chemicals production. Acidification potential was
icity and human toxicity potentials were the most significant mainly contributed by glyoxal, direct precursor in the synthesis
environmental impacts associated with “cradle to gate” Bmim of 1-methylimidazole, (30%) and butanol (40%) production

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 367–375 | 371
View Article Online

Inventory and impact analysis of NMMO synthesis

The total score of each environmental impact category (LCIA)
resulting from classification and characterization of NMMO
production is shown in Table 1. Like for Bmim Cl, global
warming, human toxicity and freshwater aquatic ecotoxicity
potentials resulted in the most significant environmental im-
pacts. For the NMMO synthesis process, the main impacts came
from the NMM production (Fig. 5), in particular from the
methanol and diethylene glycol synthesis. The only exception
was the ODP category, where the contribution of H2 O2 was
about 80%. Like Bmim Cl, the abiotic depletion was due to
fossil fuels consumption for energy and chemicals production.
Acidification potential was shared between methylamine (about
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

30%) and diethylene glycol (about 30%) syntheses due to sulfur

and nitrogen oxides air emissions. Eutrophication potential was
generated by the synthesis of diethylene glycol (about 70%), due
to the chemical oxygen demand and nitrogen oxides emissions.
FAETP was completely generated (over 95%) by industrial
effluents from diethylene glycol production. The global warming
impact, GWP, was primarily caused by the production of
hydrogen peroxide (about 40%) and of NMM (about 50%) and
it was mainly due to CO2 emission to air. The human toxicity
impact, HTP, was almost entirely associated to the sulfur dioxide
emission to air in the production of diethylene glycol (about
90%). For photochemical ozone creation, terrestrial ecotoxicity
Fig. 5 Solvent production of Bmim Cl (upper panel) and NMMO and VOCs emission potentials, the contribution of NMM was
(lower panel): contribution to LCIA of the solvent manufacturing always higher than 65%.
process (S.M.P.) and the direct precursor syntheses on each of the 10
environmental categories: abiotic resources depletion (ADP), acidifica-
tion potential (AP), eutrophication potential (EP), freshwater aquatic Comparative LCA of the cellulose dissolution methods
ecotoxicity potential (FAETP), global warming potential (GWP),
human toxicity potential (HTP), ozone depletion potential (ODP), Both impact profiles resulting from 1 kg cellulose dissolution
photochemical ozone creation potential (POCP), terrestrial ecotoxicity with Bmim Cl and with NMMO/H2 O are presented in Table 2.
potential (TETP) and emission of volatile organic compounds (VOC). Results showed the large impact in global warming for both the
solvents (3.7 kg and 3.5 kg of CO2 , respectively). Human toxicity
(0.22 kg and 0.23 kg of 1,4 dichlorobenzene equivalent, DCB-
principally due to sulfur and nitrogen oxides air emissions. eq, respectively) and freshwater ecotoxicity (about 0.12 kg and
Eutrophication potential was almost entirely generated by 0.06 kg of DCB-eq, respectively) also showed significant impacts.
the synthesis and precursors of 1-methylimidazolium (about It must be underlined that the scores reported in Table 2 do not
80%), largely due to emission to air of nitrogen oxide, and take into account the contribution from the common phases of
emission to water of ammonia and nitrogen ions (from the the two alternative dissolution processes, since they were not
wastewater treatment). Freshwater aquatic ecotoxicity potential included in the LCI.
derived almost exclusively from 1-methylimidazolium synthesis Relative comparisons between Bmim Cl (white bar) and
(about 99%) mainly due to discharge of formaldehyde into the NMMO/H2 O (grey bar) dissolution processes were made for
wastewater. Also terrestrial ecotoxicity potential derived for a each environmental impact, with the first one set as 100% and
large part (about 80%) from 1-methylimidazolium synthesis and the other displayed as the level relative to the former (Fig. 6). The
in particular from formaldehyde emissions. In GWP glyoxal environmental impacts of Bmim Cl and NMMO/H2 O dissolu-
production was the first responsible (about 30%) of the impact. tion processes were nearly of the same order of magnitude for
Regarding the emissions, CO2 was the main impact followed by all the impact categories. All categories, except human toxicity,
VOCs, methane and hydrocarbons (HC). Human toxicity was had somehow higher impacts for dissolution with Bmim Cl than
mostly caused by airborne emissions of non-methane VOCs with NMMO/H2 O. Generally, the differences in impacts were
(NMVOC), mainly from the ethylene glycol (about 56%) and under 25%. Abiotic depletion, acidification, eutrophication,
butanol (about 20%) syntheses. Also ozone depletion potential global warming, human toxicity, ozone depletion and terrestrial
derived almost exclusively from 1-methylimidazolium (over ecotoxicity impact scores of the two processes are essentially
90%). Photochemical ozone creation potential was mainly due equal. On the contrary, freshwater ecotoxicity, photochemical
to the synthesis and precursors of 1-methylimidazolium (about ozone creation and VOCs emission were about 50% 30% and
65%), in particular to formaldehyde and hydrocarbon emissions. 30%, respectively, lower for dissolution with NMMO/H2 O than
VOCs emissions mainly derived from 1-methylimidazolium the dissolution with the IL. Looking at these findings, it is
(about 60%) and 1-chlorobutane (about 30%). interesting to note that VOCs emission, known as completely

372 | Green Chem., 2011, 13, 367–375 This journal is © The Royal Society of Chemistry 2011
View Article Online

Table 2 Characterization results for 1 kg of the dissolved cellulose through NMMO-process and Bmim Cl-process

Total score
Impact category Bmim Cl-process NMMO-process Unit

Abiotic resources depletion (ADP) 9.1E-03 7.7E-03 kg Sb-eq

Global warming potential (GWP) 3.7E+00 3.5E+00 kg CO2 -eq
Ozone depletion potential (ODP) 7.7E-08 7.7E-08 kg CFC11-eq
Human toxicity potential (HTP) 2.2E-01 2.3E-01 kg DCB-eq
Acidification potential (AP) 9.4E-03 8.7E-03 kg SO2 -eq
Eutrophication potential (EP) 1.8E-03 1.8E-03 kg PO4 3- -eq
Photochemical ozone creation potential (POCP) 1.1E-03 7.6E-04 kg C2 H-eq
Freshwater aquatic ecotoxicity potential (FAETP) 1.2E-01 5.6E-02 kg DCB-eq
Terrestrial ecotoxicity potential (TETP) 5.6E-03 5.5E-03 kg DCB-eq
Volatile organic compounds (VOCs) 5.2E-03 3.7E-03 kg
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

Fig. 6 Comparison of the environmental impacts due to the cellulose

dissolution with NMMO/H2 O (grey bar) and with Bmim Cl (white Fig. 7 Characterization results for 1 kg of the dissolved cellulose
bar) on each of the 10 environmental categories: abiotic resources through Bmim Cl assuming four different scenarios of solvent recovery
depletion (ADP), acidification potential (AP), eutrophication potential rate (99%, 95%, 90% and 85%).
(EP), freshwater aquatic ecotoxicity potential (FAETP), global warming
potential (GWP), human toxicity potential (HTP), ozone depletion
potential (ODP), photochemical ozone creation potential (POCP),
an important task for chemical engineers to minimize burden
terrestrial ecotoxicity potential (TETP) and emission of volatile organic upon the environment.
compounds (VOC). Some remarks on toxicity and biodegradability of Bmim Cl
appear necessary although: 1) we have preformed a cradle to
irrelevant during the IL use phase, results in significant extending gate analysis and the human- and eco-toxicity of both solvents
the system boundaries. The similar environmental balances was not included in the balance; 2) a very high recovery of
of the two cellulose solution processes gave evidence of the Bmim Cl from cellulose dissolution process can be reasonably
potential environmental suitability of the process with Bmim hypothesized and 3) its potential impact on aquatic ecosystems
Cl. As a matter of fact, many environmental advantages of could be significantly reduced by adequate management of the
NMMO/H2 O process are common to dissolution with Bmim industrial wastewaters. At first, volatility of this ionic liquid
Cl: high recovery of solvent and highly concentrated cellulose would prevent atmospheric emissions, therefore the most signif-
solutions,45 no generation of dangerous by-products like as H2 S, icant source of exposure should be the liquid emission. Secondly,
CS2 and heavy metals, very simple and relatively short processes Bmim Cl is less toxic than other ionic liquids, but in any case its
(less than 8 h, in comparison with the more than 40 h of the toxicity is higher than that of common organic solvents (such as
conventional viscose Rayon process) which involve a general acetone, methanol, ethanol, etc.) and comparable to toxicity of
reduction of electric energy consumptions. On the other hand, chlorinated organic compounds (such as dichloromethane and
some advantages of NMMO/H2 O are not common to Bmim chloroform).48 Finally, 28 day tests of biodegradability in water
Cl, i.e. low toxicity and relative biodegradability.4 have shown Bmim Cl as not biodegradable.49 All these evidences
The influence of solvent recovery is studied through a sensi- indicate that emissions of Bmim Cl in the freshwater could
tivity analysis assuming recovery rates ranging from 99% to 85% induce damages to the ecosystem and therefore their inclusion
(Fig. 7). Recoveries less than 85% are not supposed economically into boundary system could modify our results. Unfortunately,
sustainable. As it is possible to observe from the figure, the at present the lack of the characterisation factors of Bmim Cl
results are very sensitive to changes in the assumptions about for human toxicity and ecotoxicity impact categories prevent
the recovery rate. The impact categories that appear particularly its inclusion in the LCIA. So, a complete LCIA of a chemical
sensitive to this parameter are: abiotic resources depletion, process involving Bmim Cl will be possible only when its
freshwater aquatic ecotoxicity, photochemical ozone creation characterisation factors will be available. In any case, in order to
and emission of VOCs. These results show that the solvent attempt a preliminary evaluation, we have carried out a LCIA
recovery is a key parameter in the environmental assessment and simulation considering the emission of an equal amount of a

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 367–375 | 373
View Article Online

“surrogate compound”, the Chlormequat-chloride,50 present in contribution of cellulose dissolution process was about 10% for
the database and with ecotoxicity similar to that of Bmim Cl.51 both methods. The contribution to abiotic resource depletion
In this way, the total score of freshwater aquatic ecotoxicity was mainly due to the extraction of fossil fuels, in particular
potential shows a weak enhancement, increasing of about 4%. methane, used to electric and thermal energy production and
Obviously, in future, more consolidate data will permit less due to crude oil and methane as raw materials for organic
uncertain conclusions. solvent syntheses. In the same way, the contribution of solvent
Besides the overall impact profiles, a more detailed study production to the total score of VOCs emission was about 50%
for each impact category was performed in order to explore and 30% for Bmim Cl and NMMO/H2 O dissolution process,
the relative contribution of the four main groups of processes respectively.
in the lifecycle chain: 1) cellulose pulp production, 2) solvent The results provided evidence that solvents production in-
production, 3) transport and 4) cellulose dissolution process. volved in Bmim Cl dissolution system contributed significantly
Fig. 8 shows the relative contribution of the four sub-processes also to freshwater ecotoxicity (about 50%) and to photochemical
for dissolution with Bmim Cl and NMMO/H2 O; the dominance ozone creation (about 40%). The main contribution to photo-
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

of cellulose pulp production and the irrelevance of transport chemical oxidants formation was the emission of formaldehyde
were clear in almost all the impact categories under study for and HC related mainly to 1-methylimidazolium (about 64%),
both the dissolution methods. The low contribution of trans- in particular to glyoxal production (about 43%). In the same
portation to impact scores is quite common of “cradle-to-gate” categories, the contributions of solvent production involved in
LCA studies of chemical processes.52,53 The contributions of NMMO/H2 O dissolution method are less significant (about 5%
cellulose dissolution process appeared low (<10%) for both the and little less than 10%, respectively).
methods. In any case, it is possible to observe some exceptions. Finally, it is observable that in general the percentage con-
The contribution of solvent production to the total score of tributions to each impact category score of the two cellulose
abiotic resources depletion was about 40% and 30% for Bmim dissolution processes are very similar.
Cl and NMMO/H2 O dissolution process, respectively, and the
Cradle to gate LCA analysis of cellulose dissolution with the
ionic liquid Bmim Cl pointed out the environmental potentials
and limits of the possible industrial application of this process,
that showed very promising features on laboratory scale studies
such as highly concentrated cellulose solutions, no generation
of dangerous by-products like as H2 S, CS2 and heavy metals,
simple and relatively short processes involving electric energy
By comparison with the NMMO/H2 O dissolution process,
the most friendly dissolution process already used on industrial
scale, the dissolution with ionic liquid appears promising from
an environmental point of view. The most significant increase
in environmental impacts results from photochemical ozone
creation potential, VOCs emission and freshwater aquatic
ecotoxicity. Conversely, it is possible to observe a small reduction
of toxic compound emission with Bmim Cl use.
In both cellulose dissolution processes, the major contri-
butions to the environmental impacts come from precursor
syntheses, characterized by long supply chains from natural
resources to the end product, requiring large quantities of
organic materials, energy and solvents and involving harmful
emissions in air and water. As a matter of fact, syntheses of both
Bmim Cl and NMMO show significant environmental impacts
for many of the categories of impact chosen. For Bmim Cl, major
contributions come from the starting materials in the synthetic
Fig. 8 Cellulose dissolution by Bmim Cl (upper panel) and by NMMO pathway to imidazolium cation, in particular from glyoxal and
(lower panel): contribution to LCIA of the four sub-processes transport, formaldehyde synthesis and use. Thus, in the scale-up process
cellulose pulp production, solvent production and cellulose dissolution
of a possible future industrial application, the recycling of the
process (C.D.P.) on each of the 10 environmental categories: abiotic
solvent appears a crucial point that could highly mitigate the
resources depletion (ADP), acidification potential (AP), eutrophication
potential (EP), freshwater aquatic ecotoxicity potential (FAETP), global environmental impacts coming from its synthesis and from the
warming potential (GWP), human toxicity potential (HTP), ozone cellulose extraction-transformation phase.
depletion potential (ODP), photochemical ozone creation potential These results encourage further investigation on the use of
(POCP), terrestrial ecotoxicity potential (TETP) and emission of volatile ionic liquids in the dissolution and derivatisation processes of
organic compounds (VOC). cellulose and wood and confirm that to evaluate the “greenness”

374 | Green Chem., 2011, 13, 367–375 This journal is © The Royal Society of Chemistry 2011
View Article Online

of a product or process it is necessary to consider the impacts 25 R. Hischier, Life cycle inventories of packaging and graphical paper.
over the entire life cycle so avoiding problem-shifting from one Final report ecoinvent Data v2.0 No. 11, Swiss Centre for Life Cycle
Inventories, Dübendorf, 2007.
life cycle stage to another, from one geographic area to another, 26 R. Frischknecht, N. Jungbluth, H. J. Althaus, G. Doka, R. Dones,
and from one environmental medium to another. T. Heck, S. Hellweg, T. Heck, R. Hischier, T. Nemecek, G. Rebitzer
and M. Spielmann, Int. J. Life Cycle Assess., 2004, 10(1), 3–9.
27 G. Geisler, T. B. Hofstetter and C. K. Hungerbühler, Int. J. Life Cycle
Acknowledgements Assess., 2004, 9(2), 101–113.
28 R. Hischier, S. Hellweg, C. Capello and A. Primas, Int. J. Life Cycle
We acknowledge the ministry MiUR and the University of Assess., 2005, 10(1), 59–67.
Bologna (Polo Scientifico Didattico di Ravenna and RFO) 29 R. K. Sinnott, Coulson & Richardson’s Chemical Engineering Volume
for funding. The authors wish to thank Dr E. Scimia (Febe 6, Third edition, Butterworth-Heinemann, 1999, Oxford, UK.
30 W. D. Baasel, Preliminary chemical engineering plant design 2nd ed.,
Ecologic) for her kind assistance during GABI 4 software Van Nostrand Reinhold, 1990, New York, NY.
implementation and operation and Dr L. Galasso for data 31 T. E. Casavant and R. P. Côte, J. Clean. Prod., 2004, 12, 901–908.
processing and collaboration. 32 D. A. Glasscock and J. C. Hale, Chem. Eng., 1994, 101(11), 82–
Published on 24 December 2010. Downloaded on 2/26/2019 4:31:02 AM.

33 Aspen Plus,R 10.2-1, Aspen Technology, Burlington, Massachusetts

References (USA), 2000.
34 J. B. Guinée, M. Gorrée, R. Heijungs, G. Huppes, R. Kleijn, A. de
1 R. Kotek, in Handbook of fiber chemistry, Taylor & Francis Group, Koning, L. van Oers, A. Wegener Sleeswijk, S. Suh, H. A. Udo de
LLC, 2006, pp. 678-771. Haes, H. de Bruijn, R. van Duin, M. A. J. Huijbregts, E. Lindeijer,
2 B. Łaszkiewicz, A. C. G. M. Lodart and S. A. Łódź, Poland, 1997. A. A. H Roorda, B. L. Van Der Ven and B. P. Weidema, Life cycle
3 H. Firgo, M. Eibl and D. Eichinger, Lenzinger Berichte, 1995, 75(96), assessment: an operational guide to the ISO standards: Parts 1 and 2,
47–50. Ministry of Housing, Spatial Planning and Environment (VROM)
4 G. Meister and M. Wechsler, Biodegradation, 1998, 9(2), 91–102. and Centre of Environmental Science (CML), Den Haag and Leiden,
5 T. Rosenau, A. Potthast, H. Sixta and P. Kosma, Prog. Polym. Sci., The Netherlands, 2001.
2001, 26(9), 1763. 35 S. Park and R. J. Kazlauskas, J. Org. Chem., 2001, 66, 8395–8401.
6 M. J. Earle and K. R. Seddon, ACS Symp. Ser., 2002, 819(2), 10–25. 36 Hydrocarbon Processing, The Leonard Process Company, 1979, vol.
7 P. Wasserscheid and T. Welton, in Ionic liquids in synthesis, Wiley- 58, (issue 11), p. 194ff.
VCH, Weinheim, 2nd edn, 2007. 37 M. W. Forkner, J. H. Robson and W. M. Snellings, in Kirk-Othmer
8 T. Welton, Chem. Rev., 1999, 99, 2071–2083. Encyclopedia of Chemical Technology, Forth Edition, Wiley, New
9 V. I. Parvulescu and C. Hardacre, Chem. Rev., 2007, 107, 2615–2665. York, 1994, vol.12, p. 695.
10 H. Zhao, Chem. Eng. Commun., 2006, 193, 1660–1677. 38 G. Mattioda and A. Blanc, in Ullmann’s Encyclopedia of Industrial
11 N. V. Plechkova and K. R. Seddon, Chem. Soc. Rev., 2008, 37, 123– Chemistry, Fifth Edition, Verlag Chemie, Weinheim, New York,
150. 1989, vol. A12, p. 491.
12 E. F. Borra, O. Seddiki, R. Angel, D. Eisenstein, P. Hickson, K. R. 39 GB Patent, 1 272 592, 1963.
Seddon and S. P. Worden, Nature, 2007, 447, 979–981. 40 K. Ebel, H. Koehle, A. Gamer and R. Jäckh, in Ullmann’s Encyclope-
13 R. Swatloski, S. Spear, J. Holbrey and R. Rogers, J. Am. Chem. Soc., dia of Industrial Chemistry, Fifth Edition, Verlag Chemie, Weinheim,
2002, 124, 4974–4975. New York, 1989, vol. A13, p. 661.
14 S. Zhu, Y. Wu, Q. Chen, Z. Yu, C. Wang, S. Jin, Y. Ding and G. Wu, 41 A. von Daniken and M. Chudacoff, Vergleichende okologische
Green Chem., 2006, 8, 325–327. Bewertung von Anstrichstoffen in Baubereich – band 2: Daten. Buwal
15 J. Mikkola, A. Kirilin, J. Tuuf, A. Pranovich, B. Holmbom, L. Kustov, Schriftenreihe Unwelt Nr 232, Buwal, Bern, 1995.
D. Murzin and T. Salmi, Green Chem., 2007, 9, 1229–1237. 42 US Patent, 4 748 241, 1988.
16 H. Zhang, J. Wu, J. Zhang and J. He, Macromolecules, 2005, 38, 43 US Patent, 5 917 039, 1999.
8272–8277. 44 US Patent, 4 246 221, 1981.
17 Y. Fukaya, K. Hayashi, M. Wada and H. Ohno, Green Chem., 2008, 45 B. Kosan, C. Michels and F. Meister, Cellulose, 2008, 15, 59–66.
10, 44–46. 46 D. Kralisch, A. Stark, S. Körsten, G. Kreisel and B. Ondruschka,
18 I. Kilpeläinen, H. Xie, A. King, M. Granstrom, S. Heikkinen and D. Green Chem., 2005, 7, 301–309.
Argyropoulos, J. Agric. Food Chem., 2007, 55, 9142–9148. 47 Y. Zangh, B. R. Bakshi and E. S. Demessie, Environ. Sci. Technol.,
19 D. Fort, R. Remsing, R. Swatloski, P. Moyna, G. Moyna and R. 2008, 42(5), 1724–1730.
Rogers, Green Chem., 2007, 9, 63–67. 48 T. P. Thuy Pham, C.-W. Cho and Y.-S. Yun, Water Res., 2010, 44,
20 J. Anderson, J. Ding, T. Welton and D. Armstrong, J. Am. Chem. 352–372.
Soc., 2002, 124, 4974–4975. 49 D. Coleman and N. Gathergood, Chem. Soc. Rev., 2010, 39, 600–637.
21 J. Vitz, T. Erdmenger, C. Haensch and U. Schubert, Green Chem., 50 Cycocel R Extra BASF, Safety data Sheet, Version 1.0, revision date
2009, 11, 417–424. 2009/03/18.
22 ISO 14044. Environmental management – life cycle assessment – 51 R. J. Bernot, M. A. Brueseke, M. A. Evans-White and G. A.
requirements and guidelines; 2006. Lamberti, Environ. Toxicol. Chem., 2005, 24, 87–92.
23 ISO 14040. Environmental management – life cycle assessment – 52 S. Gonzales-Garcia, A. Hospido, M. T. Moreira, J. Romero and G.
principals and framework; 2006. Feijoo, J. Clean. Prod., 2009, 17, 1010–1016.
24 GaBi software-system and databases for life cycle engineering, ver. 4.3, 53 C. Jimenez-Gonzales, A. D. Curzons, D. J. C. Constable and V. L.
PE International, Stuttgart, Germany, 2002. Cunningham, Int. J. Life Cycle Assess., 2004, 9, 114–121.

This journal is © The Royal Society of Chemistry 2011 Green Chem., 2011, 13, 367–375 | 375