www.rsc.org/greenchem PAPER
Comparative cradle-to-gate life cycle assessments of cellulose dissolution
with 1-butyl-3-methylimidazolium chloride and
N-methyl-morpholine-N-oxide
Serena Righi,*a Andrea Morfino,a Paola Galletti,a Chiara Samorı̀,a Alessandro Tugnolib and
Carlo Stramigiolib
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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).
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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
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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.
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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
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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
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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)
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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)
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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
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“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-
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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
Conclusions
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
saving.
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”
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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.
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