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Friedrich Schiller University of Jena, Institute of Pharmacy, Department of Pharmaceutical Technology, Otto-Schott-Str. 41, D-07745 Jena, Germany. E-mail: email@example.com; Fax: +49 3641 949942; Tel: +49 3641 949951
First published on 15th September 2014
The implementation of Life Cycle Assessment and related methods in green chemical process and synthesis design strongly supports the development of greener concepts on the basis of deep and profound insights into the dependences between the selection of compounds and process parameters and the resulting environmental impacts. This review article provides an overview on things to know about LCA in general, specifics to be considered during its application in the field of chemical (re-)designs and current application examples from emerging research areas such as active pharmaceutical ingredient manufacturing, nanotechnology, flow chemistry, process intensification under harsh synthesis conditions, process integration, waste treatment, the use of alternative energy sources or solvents as well as chemistry based on renewable resources.
Dana Kralisch
Dr Dana Kralisch studied environmental chemistry at the Friedrich Schiller University of Jena, Germany. In 2006, she obtained her PhD degree and became a research group leader at the Institute of Technical Chemistry and Environmental Chemistry, FSU. During her time at ITUC, her research activities focused on green chemical and biotechnological process design supported by LCA and enabling technologies. In 2012, Kralisch founded her own biotech company and started in parallel her work at the Department of Pharmaceutical Technology at FSU. Her research group is currently engaged in green pharmacy and bio-based material development for medical applications.
Denise Ott
Dr Denise Ott studied chemistry at the Friedrich Schiller University of Jena, Germany. In 2009, she received her PhD funded by a German Federal Foundation for the Environment (DBU) dissertation fellowship, dealing with the ecological and economic evaluation of the synthesis and application of ionic liquids in the context of their classification as green solvents. Within her postdoctoral research activities at FSU she is engaged in several national and European projects dealing with process evaluation, redesign and optimisation using life cycle based approaches and risk assessment tools. In 2014, she turned in parallel to TU Eindhoven, Netherlands.
Doerthe Gericke
Dörthe Gericke studied chemistry and environmental chemistry at the University of Potsdam and the Friedrich Schiller University of Jena. She obtained her masters degree in the Kralisch group focusing on the Life Cycle Analysis of catalytic process alternatives. Throughout her studies, she has volunteered as well in various sustainability activities beyond the chemical approach. She is now working on her PhD in organic chemistry at the University of Potsdam.
But, how can the environmental impact of a novel chemical process or material design be determined in a quantitative manner right from the start to support sustainable developments? Over the past few decades, the concept of life-cycle thinking has become increasingly important. Consequently, the method of Life Cycle Assessment (LCA)1,2 has been developed and is now established as one of the major tools for the analysis of anthropogenic environmental impacts.3 LCA is outstanding in its scope of applicability and its holism. It considers the whole life cycle of a product or process and evaluates environmental impacts in terms of various environmental impact categories that go beyond the consideration of mass or energy flows.
LCA was developed in the early seventies and has since then been refined and supported with inventory databases and impact assessment methodologies. Today, it can be applied to very complex issues. Aiming to compare the eco-friendliness of products and processes, LCA is nowadays an integral part of decision-making in industry and governmental and non-governmental organisations. LCA can be used as a standalone tool or in combination with other environmental, risk, economic or social assessment tools, see also the reports by Jacquemin et al.3 or Guinée et al.4 and the references therein.
For those who want to learn more about the methodological aspects of LCA investigations during chemical process and synthesis design, this review article provides an introduction into the topic, indicating further interesting literature to read on. Against the background of the LCA theory, recent case studies derived from emerging research areas such as active pharmaceutical ingredient manufacturing, nanotechnology, flow chemistry, process intensification by harsh synthesis conditions, process integration, waste treatment, the use of alternative energy sources or solvents as well as chemistry based on renewable resources are presented, emphasising the usefulness and importance of LCA in today's green chemical design.
The defined structure of LCA studies consists of the following stages: (i) Goal and Scope Definition, (ii) Life Cycle Inventory Analysis (LCI), (iii) Life Cycle Impact Assessment (LCIA), and (iv) Life Cycle Interpretation. LCA is usually an iterative process. While working at one of the stages, difficulties in the acquisition of data might appear or new information may give rise to a necessary change in the settings made previously. Thus, it is often useful and necessary to go back to earlier stages and change these settings.5
In the case of a process involving more than one commercially useful product as well as recycled materials, an allocation of the energy and material flows has to be applied.5 In general, various allocation methods are present and are controversially discussed.7–9 Two of the more common allocation procedures refer to the mass or market-value of these products (see Fig. 2).
The impact categories are selected according to the goal and scope of the study. The category indicator is the quantifiable representation of a certain impact category. The category indicator and the characterisation model are developed according to the environmental mechanism that is known for the particular impact category. The potential environmental impacts of the elementary flows that are identified in the LCI are classified within these impact categories. During characterisation, the potential impact of an inventoried item is quantified in terms of a representative unit, e.g., in carbon dioxide equivalents in the case of emissions causing climate change. The normalisation step is the calculation of the characteristic value of the category indicator relative to a reference value, e.g., in relation to an emission limit or per capita. The normalisation step is optional and does not have to be included in the LCIA.5
There are two different kinds of impact categories, the input- and the output-related categories. The theoretical model behind an input-related category could be described as follows: if the elementary flow is the extraction of 1 kg mineral oil, the effect (and the indicator) will be the depletion of a particular share of the remaining fossil oil resources. In order to define the impact of this depletion the scarcity, the renewability and the availability of a resource have to be considered. Therefore the evaluation of input-related indicators is already a complex issue.11 The output-related categories are even more difficult to quantify, because the effects of the outputs are more multi-layered. There are primary, secondary and tertiary (and even more) effects of an output that can all serve for the indication of the characterisation. For the impact category of Climate Change (CC) the effect chain could be described as follows:
(i) Primary effect: increase of the concentration of gases in the atmosphere that absorb radiation (the indicator here could be the measured value of the relevant gases).
(ii) Secondary effect: increase of the temperature.
(iii) Tertiary effect: variations in climate (different effects on the climate in different regions of the world): higher temperature peaks (cooler and warmer) drought, storms.
This list can be continued with further possible effects such as changes in abiotic conditions, effects on living nature and eventually, effects on human health. If the indicator of a certain impact category is close to the inventory (close to the emission), it is called a midpoint indicator. If the indicator is describing a tertiary effect, it is called an endpoint indicator. As shown in Fig. 3, the indication of the effects becomes more complex due to the chain of events between cause and effect. Tertiary effects and beyond are difficult to measure and the number of impact categories rises, since the emission of one substance often has multiple effects (for example considering different areas of protection). Still, the use of endpoint categories would describe the actual impacts that the areas of protection are affected by, rather than the changes of the environment that result in potential effects. Therefore, the implementation of endpoint categories is one of the major goals of the current progress of LCA methodology, but cannot be recommended without objections yet.12
|Fig. 3 Illustration of a harmonised midpoint–endpoint model for climate change, linking to human health and ecosystem damage applied within ReCiPe.10
The characterisation model, which is the foundation of the association of the LCI results with the LCIA results, is based on confirmed scientific insight. Still, the resulting impacts should not be interpreted as verified predictions. Often, the environmental mechanism is complex and the theoretical models do not include spatial or temporal dimensions.13 The assessment of impacts is always a balancing act between scientific precision and feasibility. Therefore the results of the LCIA are afflicted with uncertainties (that are often not defined, yet) and should be seen as statements on the potential impacts.
The ISO standards EN ISO 14040 and 140445 also refer to the analysis of the data quality as a mandatory part of the LCIA. Since it is part of the Life Cycle Interpretation as well, it is further explained in the next section.
One of the most up-to-date LCIA methods today is ReCiPe.10 The focus during the development of this method was on the compatibility of mid- and endpoint methods in terms of the assumptions that create the measures defined in the model. ReCiPe is a combination of the established CML 2002 and the Eco-Indicator 99 methods. At the midpoint-level, ReCiPe consists of the following 18 impact categories:
1. Climate Change (CC)
2. Ozone Depletion (OD)
3. Terrestrial Acidification (TA)
4. Freshwater Eutrophication (FE)
5. Marine Eutrophication (ME)
6. Human Toxicity (HT)
7. Photochemical Oxidant Formation (POF)
8. Particulate Matter Formation (PMF)
9. Terrestrial Eco-Toxicity (TET)
10. Freshwater Eco-Toxicity (FET)
11. Marine Eco-Toxicity (MET)
12. Ionising Radiation (IR)
13. Agricultural Land Occupation (ALO)
14. Urban Land Occupation (ULO)
15. Natural Land Transformation (NLT)
16. Water Depletion (WD)
17. Mineral Resource Depletion (MRD)
18. Fossil Fuel Depletion (FD)
To give an impression of the way the impact assessment works, the category Climate Change (CC) is further described in the following section. A description of the other 17 category indicators can be found in the ReCiPe main report.10
The impact category CC summarises the effects of elementary output substances that contribute to global warming. The calculation of the Global Warming Potential (GWP) of a certain substance appearing in the LCI is performed by the use of equivalence factors that have been defined in the report of the Intergovernmental Panel on Climate Change (IPCC).17 These equivalence factors are calculated according to the following equation:10
The term ax describes the power of the substance x to increase the radiative forcing and the term x(t) describes the lifetime of the gas, as the gases in the atmosphere are subjected to different kinds of effects that influence their concentrations, like chemical reactions with other gases or degradation caused for example by UV-radiation. As can be seen from the equation, the quality that is used to describe the CC is the increase of radiative forcing caused by a greenhouse gas relative to a reference gas. In this case, the reference gas is CO2, the most important anthropogenic greenhouse gas.18 The direct relative radiative forcing per ppbv (part per billion, volume basis) is derived from infrared radiative transfer models based on laboratory measurements of the molecular properties of each substance and considering the molecular weights.10 Originating from the IPCC, the characterisation model is consensus-based and undisputed. It is classified satisfactory and recommended by the Joint Research Centre of the European Commission (JRC). Table 1 gives an overview of the characterisation model for CC. Since most production processes are connected with a significant energy demand causing additional environmental impacts, the Cumulative Energy Demand (CED) was established as a LCIA category nearly twenty years ago.19,20
|Impact category
|Climate change
|LCI results
|Greenhouse gases
|Characterisation model
|Baseline model of 100 years as in IPCC17
|Category indicator
|Infrared radiative forcing
|Characterisation factor
|Global warming potential (kg CO2-eq. per functional unit)
|Environmental relevance
|Infrared radiative forcing is a proxy for potential effects on the climate, depending on the integrated atmospheric heat absorption caused by emissions and the distribution over time of the heat absorption
CED represents the energy demand during the entire life cycle of a product or process, and is nowadays accepted as a suitable screening indicator, predicting environmental burdens of production21 and reflecting many of energy-related life cycle impacts typically considered in an LCA study, e.g., global warming, resource depletion or acidification.22
During the early stages of green fine chemical process design, the Finechem software tool by Wernet et al.23,24 can be used for CED estimation, with a detailed LCI modelling. The related Cumulative Exergy Demand (CExD) depicts instead the total exergy removal from nature to provide a product, summing up the exergy of all resources required.25
Some years ago, the group of Dewulf and colleagues developed the more sophisticated LCIA category Cumulative Exergy Extraction from the Natural Environment (CEENE) for the impact assessment of process alternatives with a high share of energy supply on the overall environmental impacts.26 Exergy data on fossils, nuclear and metal ores, minerals, air, water, land occupation, and renewable energy sources were taken into account as "taken away" from natural ecosystems. They applied this measure also in the context of life-cycle based evaluation of pharmaceutical processes.27,28
(i) Identification of significant issues.
(ii) Evaluation.
(iii) Conclusions.
The identification of significant results is mainly achieved by structuring the results of the LCI and LCIA. The evaluation is concerned with the completeness of the data base, the consistency of the data (data quality indication) and the analysis of the sensitivity of the results for changes in data. Having checked for these criteria, conclusions can be drawn concerning the resulting recommendations but also the limitations of the LCA study.
Furthermore, unclear definitions, the cut-off of relevant up- and downstream processes, the choice of unsuited environmental impacts, and incorrect interpretations, e.g., caused by overdone aggregation, or the combination of data from different temporal or geographic origin may affect the overall LCA, thus weakening the powerful validity and reliability of life cycle analyses compared to simple green metrics. It is the responsibility of each evaluator to reduce these causes for uncertainty carefully without losing sight of practicability and to document the quality of the data used. One approach to reduce the data gathering effort is sensitivity analysis based on expert knowledge. As an example, a variation of the typical synthesis or process parameters and the analysis of the resulting effect on the overall environmental balance support the selection of most influencing process modules.29,30 In the next step, those process modules can be evaluated in more detail than others showing only a minor contribution.
Monte Carlo simulations can further help to determine whether the calculated differences between alternatives evaluated within a comparative LCA are significant. The method relies on repeated stochastic calculations within a mostly pre-defined uncertainty band in order to obtain the distribution of the unknown probabilistic entity (e.g.ref. 31 and 32).
(i) Completeness.
(ii) Temporal correlation.
(iii) Geographical correlation.
(iv) Further technological correlation.
(v) Reliability.
The data quality is evaluated by giving scores to each data set (forming the lines of the matrix) for each of these categories (the columns of the matrix). Every score is defined beforehand, and only if all the criteria in this definition are fulfilled a particular score can be assigned. The Pedigree matrix system for qualitative assessment of data quality within LCA studies has been modified and used for many different LCA studies in the past, but mostly not in the context of chemical process and synthesis design. Table 2 shows a modified pedigree matrix applicable to data quality indication for this specific application.
|Complete data including information on masses, energies, by-products and recycling
|Nearly complete data, data gaps filled with qualified assumptions
|Incomplete data, gaps filled with qualified assumptions
|Incomplete data, important data gaps filled with standard assumptions
|Incomplete data, data gaps not filled
|Primary experimental data from the research area under study, provided by experts, recent time period
|Data from area under study, from experts related to the topic of the study, from one time period
|Data from a currently conducted procedure, from the area with similar synthesis conditions, technology that could be applied
|Data from the former production procedure, area or different production conditions and technology of different scale
|Data age older than 20 years or unknown, unknown area and unknown or inapplicable technology
|Data based on repeated measurements
|Data based on measurements or calculated from trustworthy models
|Data based on the literature or on models
|Data based on qualified estimations
|Data based on non-qualified estimation or unknown origin
One major difference between Weidema's established valuation system and the one introduced here is the aggregation of the indicators for time, space and technological correspondence into one indicator called representativeness. Weidema reasons that the division is useful in order to figure out areas for improvement more easily. Nevertheless, in the early stages of chemical process or synthesis design the simplification suggested herewith has been found useful for purposes of clarity, and last but not least, due to typically limited information about the time, space and technological implications of the novel process or material under development in a future industrial environment. The indicator score is always guided by the single aspect that scores the worst. If, for example the time-correlation scores '1' and the technological correlation scores '5' or is unknown, the score for representativeness is '5'.
Thanks to the development of this method in the last 40 years there is a set of guidelines available for it that provides precise information on implementation.13 These guidelines take care of the consistency and the transparency of LCA.
The LCA approach ensures the avoidance of a problem by shifting to other stages of the process (e.g. raw material production, waste treatment) because of its comprehensiveness. When selecting the system boundaries in a life-cycle-way of thinking, the increase of environmental impacts outside these boundaries is avoided.
The evaluation of products or processes in an LCA is typically performed in a relative way. In the case of comparative studies this can mean that completely different amounts of different chemical compounds that are needed to serve the same purpose can be compared.
Nevertheless, the decisions that follow the conduct of a LCA study are still a matter of values and opinions.
The handling of uncertainties or data gaps of the study as well as the securing of comparability of alternatives are important criteria, whether the study is conducted in a scientific way. Only the precise definition of rules, the scientific discourse concerning the methodology, the scientific base of the impact assessment and, finally, the transparency of each individual LCI data set ensure the high quality of LCA studies.
As mentioned before, the LCA method is not specially designed for the evaluation of chemical processes or its application for decision-making purposes during process design (for more detailed information see ref. 34). Thus, the practitioner has to select from the high number of LCA approaches (see e.g. dynamic LCA,35 spatially differentiated LCA,36 risk-based LCA,37 environmental input–output based LCA (EIO-LCA),38 hybrid LCA39 or Eco-OptiCAD40) the best-fitting strategy without losing the holistic, comprehensive evaluation idea behind the LCA approach.
In an attempt to enable an LCA with smaller scope, the Society of Environmental Chemistry and Toxicology (SETAC) developed a framework for Simplified Life Cycle Assessment (SLCA)43 (also called Streamlined LCA), which describes the possibilities of simplification for every phase of the LCA. According to this framework, the simplification consists of three steps which are iteratively linked:
(i) Screening: identification of the elements of the LCA that can be omitted or where generic data can be used without significantly affecting the accuracy of the final result.
(ii) Simplifying: application of the simplifying options identified in the screening step to produce a simplified LCA.
(iii) Assessing reliability: making sure that results are reliable enough to justify the conclusions drawn.
These steps are intended to be applied to all four phases of the 'common' LCA, because this way the holistic approach is still ensured. Just like the 'common' LCA, the simplification is an iterative procedure. Today, a Simplified LCA is an established part of the toolbox for decision support towards more environmentally benign chemical developments.42,44
Another possibility to decrease the amount of work afflicted with LCA is to concentrate on the most relevant life cycle stages: some LCA studies are not concerned with the entire life cycle of a product, but with the potential impacts that are caused by a particular life stage (gate-to-gate analysis). More often, a cradle-to-gate assessment is performed, including all life cycle impacts caused up to the production and work-up of the final chemical compound. It is used for comparative studies evaluating different processing alternatives or synthesis pathways resulting in the same product, characterised by a comparable product quality. The further life-cycle impacts of all alternatives considered are equal and therefore excluded.
Another simplification approach was followed by GlaxoSmithKline (GSK). They developed the FLASC™ software tool45 for fast LCA in synthetic chemistry especially for Active Pharmaceutical Ingredients (API). Material classes were chosen where it was possible to generate average LCI profile data that could be used for materials where LCI data did not exist. Then, a methodology to predict the cradle-to-gate life cycle impact profile for a typical batch chemical process used to synthesise APIs was developed based on the LCI of the materials used in the process, using a combination of actual or average data, and the mass of the material. Based on a core set of life cycle impact profiles for well-developed GSK processes including separation and/or isolation steps, a series of formulae was developed that enabled a score to be calculated for different impact categories. The average FLASC™ score was finally calculated from the individual scores for each impact category. The FLASC™ tool is now used to determine, compare and benchmark the 'greenness' or relative sustainability of synthetic processes in order to facilitate more informed and sustainable business choices. The motivation for the development of this tool was again the particular high optimisation potential at an early stage in research and development (R&D) activities when route and processes are being selected and detailed environmental data are not available.
Another important issue, especially in chemical process and product design is the appropriate analysis and management of risks concerning human health, environment and safety.
That is why, LCA is sometimes coupled with risk assessment as depicted in Fig. 4 on the example of nanotechnologies.
|Fig. 4 Risk management strategy for life cycle sustainability assessment (LCSA) of nanotechnologies49 with kind permission from Springer Science and Business Media.
During early design stages, the environmental behaviour, potential hazards for humans and ecosystems of substances and their treatment when entering different environmental compartments, can be estimated using the Environmental, Health and Safety (EHS) risk assessment method.29 The EHS tool developed by Hungerbuehler and colleagues50,51 is a user-friendly approach to derive the risks resulting from the handling of chemicals. It is combinable with LCA (or Simplified LCA) and other evaluation approaches.
As mentioned before, the analysis and minimisation of future environmental impact potentials of a novel chemical process under development is most effective during early stages. This effect is contradictory to the profound data requirements of an LCA study, which usually can not be fulfilled (if no experiences with a similar process are on hand), until the process is implemented on the industrial scale. Here, process simulation tools such as ASPEN Tech and HYSYS are very helpful to estimate the mass and energy balance of the process and its optimisation potentials on the future production scale as a data basis for the LCI stage (also called ex-ante LCA).52,53
|Fig. 5 Performance matrix requiring decision support, taken from Kralisch et al.63 reproduced by permission of The Royal Society of Chemistry.
Another established method is the NP (Nonlinear Programming) approach.64 It involves the minimisation or maximisation of nonlinear objective functions subject to bound constraints, linear constraints, or nonlinear constraints.
The assessment of multi objective optimisation results can be done using the Pareto concept.65 Standardised algorithms for identifying pareto-optimal solution candidates constitute for example the basis for partial ranking (out-ranking) procedures. Fig. 6 shows a bi-objective Pareto-optimal curve (considering environmental and economic impacts). Parameter configurations and resulting impacts of alternatives at the Pareto-front cannot be changed or improved without worsening the other criterion/criteria.
In order to define a preference relation of multi-attributed alternatives, the outranking methods mentioned before can be applied. As a result of a total or partial outranking procedure regarding several LCIA results, preferences for specific, pareto-optimal options for environmental efficiency can be quantified. At this, the environmental efficiency can be determined based on the relative saving potentials in different LCIA categories referred to as the worst as well as the best case candidates (highest or lowest environmental impact potential, respectively) calculated in each of these categories. Finally, one aggregated environmental efficiency value can be calculated by means of weighting factors.72,73 Furthermore, the results are transferable to, e.g., a bi-objective eco-portfolio depiction showing environmental and cost efficiency in one graph. Thereby, cost efficiency is typically calculated taking into account relevant variable and fixed production cost criteria, e.g., investment, material, energy, personnel, and waste treatment costs. High efficiency values in both categories place attention on preferential options.
Fig. 7 shows an example of criteria contributions to the total eco-efficiency ranking of alternative biodiesel production pathways.72 Despite a lower cost efficiency of processes D and E (being supercritical, waste oil based process alternatives), their environmental efficiencies are strongly preferred in contrast to conventional processing alternatives (processes A–C). In consequence, this results in a higher ranking score and thus in a preference against the other process alternatives.
|Fig. 7 Criteria contribution (scaled) to overall eco-efficiency ranking of different biodiesel production alternatives utilising waste oil (Process A: pre-treated alkali-catalysed; Process B: acid-catalysed; Process C: heterogeneous acid-catalysed; Process D: supercritical process, Process E: supercritical, microreactor based process) according to Kralisch et al.72
|Fig. 8 Simplified demonstration of the SEECube related to the BASF SEEbalance® concept:74 consideration of environmental, cost and social impacts.
For instance, Ouattara et al.66 investigated the HAD process (hydrodealkylation of toluene) for the production of benzene focusing on an optimised criteria configuration related to costs and selected process outcome relevant life cycle impact categories in a three-dimensional evaluation.
Kralisch and co-workers76 evaluated different biodiesel production pathways using a tetrahedral chart containing environmental, safety and cost criteria, see Fig. 9. Thereby, all of the three criteria consists of a pre outranking of sub-category performance matrices (e.g., LCIA categories), resulting in a single ranking score for each criterion. The final tetrahedron emphasises not only the preference, but also the potential for further development activities in the dependency of the target criteria. If needed, a post outranking of LCA, LCC and EHS criteria can be performed by applying weighting parameters for each category, e.g., depending on target constraints or expert knowledge.
|Fig. 9 Three-dimensional criteria decision-making in the context of biodiesel manufacturing pathways. LCC: life cycle costing; LCA: life cycle assessment; EHS: environmental, health and safety risk assessment. Tetrahedral graph according to Kralisch et al.76
|Fig. 10 LCA system boundaries of the catalytic reactions investigated by van Kalkeren et al.77 published by The Royal Society of Chemistry.
The results revealed that the replacement of phosphines by silanes can result in environmental improvements for the Wittig reaction, but that additional reagents and working in lower concentrated solutions would offset potential environmental improvements for the Appel reaction.
Griffiths and colleagues applied the LCA tool to measure the performance of a range of iron and palladium based nanoparticle catalysts for carbon dioxide utilisation on the laboratory scale.78 The catalysts combined the reverse water gas shift reaction with the Fischer–Tropsch process to convert CO2 into hydrocarbons used as fuels and feedstocks for the chemical industry. The LCA results afforded insight into 'green' catalyst design, since palladium addition vastly improves catalyst performance. However, they also found scenarios in which the continual addition of palladium, although showing favourable CO2 conversion and hydrocarbon yields, does not return a sufficient environmental offset to cover the embodied impacts present in its generation.
A novel approach to a catalytic synthesis of caprolactam was studied in an ex-ante environmental assessment by Roes and Patel (see Fig. 11).79 By means of the indicators non-renewable energy use (NREU) and climate change (CC), they found that the production of caprolactam by a novel homogeneous transition metal catalyst can offer clear advantages compared to the petrochemical production of caprolactam. Furthermore, 3-pentenamide, i.e., the precursor used in the novel catalytic process could be made from bio-based, instead of petrochemical butadiene, which would further reduce the environmental impacts. The same was pointed out for the syngas, which could be produced from biomass.
|Fig. 11 Flow sheet for the novel catalytic production of caprolactam studied by LCA79 reprinted with permission from Elsevier.
The environmental as well as economic benefits of recycling and reuse of catalytic plates typically used in microreactors were checked by Kressirer and colleagues by means of LCA (CML 2002 LCIA methodology) and cost analyses.80 They found clear economic advantages, especially in the case of a combined reuse of the plates and recycling of the catalytic coatings, but the benefits to the environment were less conclusive. This was due to the additional demand for chemicals used for cleaning and recycling as well as for extra energy. Thus, further efforts for an optimisation of the overall post treatment and reuse process were required.
|Scheme 1 Two-(left) and one-step (right) production routes of adipic acid83 reprinted with permission from Elsevier.
An alternative approach was evaluated by van Duuren et al.84 They performed a Simplified LCA of a combined biological and chemical process for the production of ADA. The LCA comprises the biological conversion of the aromatic feedstocks benzoic acid, impure aromatics, toluene, or phenol from lignin into cis,cis-muconic acid, which is subsequently converted to adipic acid through hydrogenation.
Their SLCA study focused on the LCIA categories CED, CExD, and CO2 equivalent emissions (comparable to an assessment of GWP). The highest calculated reduction potential of CED and CExD was achieved using phenol from lignine, which reduced the CED up to 57% compared to a petrochemical benchmark process. The bulk of the bioprocessing energy intensity was attributed to the hydrogenation reactor, directly related to the product concentration in the broth.
In conclusion, enhanced catalytic approaches have shown their great potential for improving the greenness of chemical processes. Of course, it has to be combined with the most material and energy efficient processing in order to exploit its full potential. But this is true also for any other concept for more environmentally benign chemical processing as discussed below.
|Scheme 2 Basic ester hydrolysis of p-nitrophenyl acetate (1) to sodium p-nitrophenolate.85
Although the new process alternative requires more energy compared to experiments without ultrasonication, a Simplified LCA utilising GWP and HTP as key indicators confirmed the development of a significantly greener process (e.g., decrease of the GWP up to 80% as a result of the yield increase).
|Scheme 3 Suzuki–Miyaura reaction of aryl bromides (1) with phenylboronic acid (2) yielding biaryls (3)86 reproduced by permission of The Royal Society of Chemistry.
Nevertheless, similar results were found by Kressirer and colleagues30 for a comparative investigation of oil bath, microwave or direct electric heating, taking into account the impact categories GWP and HTP. Again, microwave heating did not result in any savings due to the low energy efficiency of the microwave apparatus (being in the range of 16–20%).
Thus, using alternative forms of energy supply will not a priori result in a greener process. However, more effects than the energy efficiency ratio have to be taken into account in order to assess the environmental impact potential derived from the decision for a form of energy supply to a chemical reaction as shown by Huebner and colleagues.85 Furthermore, if switching to continuous processing, batch technologies need to be replaced by continuously operated, time reducing modules for pre and post treatment as well. Here, microwave drying can provide an alternative technique to conventional time demanding vacuum drying, e.g., within pharmaceutical processes87,88 Pharmaceutical powders have a relatively high dielectric loss factor compared to standard solvents and can therefore efficiently be dried using microwaves89, meeting also the strict quality criteria. In such cases, life-cycle based analyses can again provide valuable support in terms of holistic decision making. The integration of CExD or CEENE analysis in future studies would further enhance the meaningfulness of a comparison taking into account alternative energy sources.
|Fig. 12 Combining the LCA and EHS50 method according to Capello et al.90 reproduced by permission of The Royal Society of Chemistry.
Luis et al.96 investigated the environmental burdens of batch and continuous distillation vs. incineration for the treatment of selected waste–solvent mixtures of different concentrations: acetonitrile–toluene, acetonitrile–toluene–tetrahydrofuran, ethyl acetate–water and methanol–tetrahydrofuran. The LCIA was performed by calculating the Eco-Indicator 99, UBP-97 (method of ecological scarcity),97 GWP, CED and CO2 emissions.96
Based on the LCA methodology, Amelio et al. further developed guidelines for solvent selection during the process design and evaluation of treatment alternatives. Therein, they investigated the environmental effect of treatment methods of 17 molecular solvents and their combined binary mixtures.93 Both papers concluded that the main impact arises from upstream processes of manufacturing these solvents. Thus, if the solvent supply is connected to high environmental burdens, a solvent distillation is preferred to its incineration. A comparison of the information, given by the different LCIA indicators used in this study, revealed that all indicators led to the same conclusions for the evaluated mixtures with some exceptions only for UBP-97.
Against the background of promising features of, e.g., non-flammability, high thermal stability or negligibly low vapour pressure, ionic liquids were uncritically referred to green chemistry at first and discussed as "green" substitutes to molecular organic solvents. Then, first results concerning their partial toxicity, production effort and environmental impact have induced a more differentiated point of view. Nowadays, the assessment of their chemical and biological properties, and the resulting environmental impacts have become important research and development aspects. Zhang et al.99 performed an LCA of the synthesis and application of an ionic liquid compared to selected molecular solvents. The authors emphasised the challenges and uncertainties of a product or process assessment in the early stages of development of a new class of compounds, but pointed out the importance of ecological evaluations of ionic liquids in contrast to other solvent systems. In consequence, they decided to perform a cradle-to-gate LCA, neglecting downstream processes, particularly due to the fact that information on industrial disposal routes and the resulting emission pathway into the environment was not available.
Reinhardt et al. performed simplified (focusing on CED evaluation in combination with EHS criteria) up to holistic LCA studies to evaluate and optimise the synthesis of selected ionic liquids, and compared their ecological performance to molecular solvents for the Diels–Alder reaction.63,98,100 The implementation of LCA strategies in ionic liquids R&D demonstrated the high optimisation potential for common synthesis strategies for these compounds and emphasised the need for a critical evaluation already at early process development stages. The life cycle impact of the ionic liquids was investigated to be much higher than that of the selected molecular solvents, see Fig. 13, primarily due to the extensive pathway of its manufacture. The authors concluded that potentially the ecological and economic impacts resulting from the manufacture can only be counter- or outbalanced within the application phase, if proper recycling is ensured and the use of ionic liquids results in an essential improvement in the application stage. However, in the case studies of metathesis101 and Diels–Alder reactions investigated98 clear environmental benefits for the use of molecular solvents were found.
|Fig. 13 Comparison of the life cycle environmental impacts of the manufacture of ionic liquids with molecular solvents according to Ott and colleagues.98
Altogether, solvent selection, reduction and recycling have become a big issue not only in academia but also in particular in industry. If this trend is continued, one very important source of environmental impacts caused by chemical and pharmaceutical industry will be distinctly reduced. Even simplified approaches, taking into account in particular energy demand and toxicological criteria in a life cycle based manner, are of great value here.
An LCA comparison of a batch versus continuous flow processing of the exothermic anionic polymerisation of styrene again resulted in environmental benefits for the flow process due to the avoidance of a cryogenic cooling system.104
|Scheme 4 Phase transfer catalysis (PTC) of benzoyl chloride and phenol evaluated by a Simplified LCA.103
An improvement of the mixing of the biphasic reaction system was realised by transferring the synthesis from batch to flow processing using different types of micromixers in combination with ionic liquids as phase transfer catalysts.
The performance of the micromixing structures was significantly influenced by the process parameters chosen, especially by the utilisation of ionic liquids such as [C18MIM]Br, [MIM][BuSO3] or [BMIM]Br as phase transfer catalysts. The ionic liquids showed strongly positive results on the yield of the esterification reaction compared to non-catalysed syntheses. Despite the high environmental burden of these compounds resulting from their material and energy demanding synthesis, the overall environmental balance was improved even when the ionic liquids were used only once without recycling. Sensitivity analyses were performed by varying relevant process parameters including the amount of solvent, the yield and flow rates. Based on this, the work-up step was found to be a major bottleneck for the green process design, independently from the decision for batch or flow processing. Another critical element was the higher energy demand of the flow processing plant including pumps and process control systems compared to the batch system. As a result, substantial savings up to 70% for the microreaction process were forecasted only under the constraint that the high electricity demand of the peripheral equipment can be reduced in an optimised production process.
These and further studies have shown that flow chemistry can provide powerful options to improve the environmental balance of chemical processes, but has to come along with benefits in yield/selectivity, energy management or solvent demand. Otherwise, the additional effort involved in increased process control will counterbalance the advantages.
|Scheme 5 Kolbe–Schmitt synthesis starting from resorcinol with a CO2-precursor giving 2,4-DHBA (target product) and 2,6-DHBA as by-product (Krtschil et al.107).
The process was intensified using a microreaction process under NPW conditions applying high temperature (up to 250 °C) and pressure (up to 120 bar). Process design alternatives and several solvent concepts were critically compared by means of a Simplified LCA in order to develop a green process (Fig. 14).30 In addition, the application of microwave irradiation instead of oil bath heating was tested in order to increase the energy efficiency of the process. As active media, hydrogen carbonate containing water or ionic liquids, supercritical CO2 as well as Dimcarb, a liquid dimethylamine:CO2 (1.8:1) adduct, were investigated under different reaction conditions (e.g., temperature, pressure, concentration and molar ratio).
|Fig. 14 Concepts for PI of Kolbe–Schmitt synthesis by Kressirer et al.30 reprinted with permission from the American Chemical Society.
The design accompanying a Simplified LCA using the LCIA methods CML 2002 and CED pointed out several hot spots for process design improvements compared to the reference, a batch process utilising aqueous KHCO3 at a reaction temperature of 100 °C under normal pressure. The application of supercritical carbon dioxide had an adverse impact on the reaction performance, but aqueous [EMIM][HCO3] or [BMIM][HCO3] led to significantly increased yields. Nevertheless, a greener process using these active solvents can only be realised in combination with an efficient recycling of these compounds.108 The authors explained this outcome with the high environmental impacts caused by the supply chain of the ionic liquids. All in all, the evaluation pointed out that the environmental balance of the Kolbe–Schmitt synthesis benefits from efficient work-up strategies and the utilisation of recyclable ionic liquids as active solvents rather than from harsh synthesis conditions or alternative forms of energy supply.
Three LCA studies were performed evaluating this topic in detail. In all cases, the same LCIA method, namely CML 2002, was used. This allows a good comparability of the results and provides the opportunity to build upon each other. At first, Morais et al. reported about the potential environmental impacts of different process design alternatives for biodiesel production from waste vegetable oils.109 The process design alternatives considered in this study included an alkali-catalysed process with a free fatty acid pre-treatment, an acid-catalysed process and a supercritical methanol process using propane as co-solvent. These processes were simulated using the process simulator ASPEN Plus®. The outcome of the study already proposed a supercritical processing of waste oil, using methanol as well as propane as co-solvents. The authors argued that although the supercritical methanol process is highly energy intensive, the downstream operation of methanol recovery and the product purification are much simpler, enabling a decrease in the overall energy consumption compared to the process alternatives with moderate reaction temperatures below 100 °C and normal pressure. An LCA study of Sawangkeaw and colleagues,110 again supported by process simulation, confirmed that supercritical processing under high temperature conditions of 400 °C can be beneficial also in the case of fresh vegetable oil (here: palm oil).
Based on this, Kralisch et al.76 recently performed a systematic LCA based decision support procedure for the best-suited process design of a biodiesel production process before a pilot plant construction. The development of the novel biodiesel production alternative was accompanied by process simulation, LCA, cost and risk analyses nearly from the beginning using an iterative evaluation procedure. They pointed out favorable process parameter combinations in parallel to experimental optimisation. The transesterification of waste oil via supercritical processing at a temperature of 380 °C and a pressure of 200 bar in intensifying continuous flow reactors was found to be the most favourable option out of eighteen and was transferred to a newly developed mini-plant design. It allows a reduction of the overall GWP up to 70% referred to the industrial established benchmark, utilising fresh vegetable oil under moderate process conditions, as well as a safe processing despite supercritical process conditions.
In summary, harsh process conditions in chemical production were found to be not per se critical for the environment. Despite the comparably high energy demand for heating, pressurizing or cooling, benefits in yield and/or simplified pre and post treatment can lead to green intensified processes.106
Recently, Patel et al. presented an early-stage sustainability assessment framework to analyse new bio-based process alternatives.112 The assessment relied on a multi-criteria approach, integrating the performance of chemical conversions based on five indicators into an index value. The indicators encompassed economics, environmental impact, hazards and risks, techno-economics and LCA. For each bio-based process, two R&D stages (current laboratory and expected future) were assessed against a comparable conventional process. The multi-criteria assessment in combination with an uncertainty and scenario analysis showed that the chemical production processes using biomass as a feedstock can provide potential sustainability benefits over conventional alternatives, but requires further development, especially in the case of biomass gasification and pyrolysis processes for fuel production.
Gerber and colleagues integrated the LCA methodology in thermo-economic process models for the conceptual design of combined fuel and electricity production from the lignocellulosic biomass.113 They formulated the LCI as a function of the design variables of the thermo-economic model and used a multi-objective optimisation algorithm to consider the environmental performance calculated by LCIA together with thermo-economic indicators as objective functions in process optimisation at an early stage of the synthesis process.
They argued that with a classical LCA approach, changes in process configuration or design conditions, effects of process integration, future installation size and technology evolution are often not considered or cannot be evaluated. Thus, typically only a few scenarios based on average technologies are discussed. The results of the study showed a non-correspondence of the thermodynamic optimum with the environmental optima, determined by means of the Eco-Indicator 9916 method (Fig. 15). The energy service substitution and therefore the increase in energy efficiency were key points for the reduction of environmental impacts, especially in the case of a process producing multiple energy services. The results of the multi-objective optimisation further highlighted the importance of the impact caused by logistics, auxiliary materials and off-site emissions associated with the process operation which are usually not accounted in a process design considering only thermo-economic objectives.
|Fig. 15 Results of multi-objective optimisation using the Eco-Indicator 99 impact as the environmental objective, biomass profitability as the economic objective, at a multiple scale113 reprinted with permission from Elsevier.
The optimal design and operation of a hydrocarbon bio-refinery via fast pyrolysis, hydrotreating and hydrocracking for crude bio-oil production was investigated by Gebreslassie and colleagues.64 The authors applied a model that seeks to maximise the economic performance measured by the net present value (NPV) and to minimise the environmental impacts, described by means of the LCIA category GWP in a gate-to-gate analysis. The Pareto curve in Fig. 16 shows the optimal trade-off of several designs of the hydrocarbon bio-refinery. Each Pareto point represents an optimal design strategy for the hydro-carbon bio-refinery with a trade-off between the economic and environmental criteria NPV and GWP. As shown in Fig. 16, relative to the maximum NPV design (point C), the global GWP can be reduced to 63% at the expense of decreasing the NPV by 43%. In the other direction, the NPV is increased if GWP is increased as well. At the trade-off point B, the best compromise between these contradictory objectives was found. The study was complemented by an extended model of the bio-refinery including a number of major processing stages, such as drying of the cellulosic biomass feedstocks, the air separation unit, gasification, syngas conditioning, the Fischer–Tropsch synthesis, hydroprocessing, power generation, and diesel and gasoline production.68
|Fig. 16 Pareto optimal curve for a hydrocarbon bio refinery64 reprinted with permission from Elsevier.
These examples, together with the case studies of utilising biomass under harsh process conditions, as discussed before, provide a mixed message. The life cycle step of agricultural biomass generation is most often connected with significant environmental impacts, dominating the overall LCA balance.
Thus, careful process optimisation for high material and energy efficiency is required to come up with the best trade-off. MCDM and MOO are tools of high value bringing forward today's approaches for biomass utilisation.
|Fig. 17 Synthesis steps and their yields for the production of Galantamine·HBr evaluated by the LCA indicator CEENE15 reproduced with permission from The Royal Society of Chemistry.
The solvent switch in particular, had an effect on the reduction of resource requirements. In the third generation of the process pathway optimisation, the sixth step was replaced by a continuous process using a flow reactor. The increased resource efficiency, by changing from the first till the third generation, resulted in a reduction of the overall resource consumption up to 41%, realised by new chemistry in combination with flow processing.
|Fig. 18 Multi-criteria outranking of API production alternatives according to their environmental and cost efficiency compared to the existing process AP; criteria weights: equal, linear minimisation of LCIA criteria and costs73 reproduced with permission from The Royal Society of Chemistry.
These case studies show that the high effort required in the case of LCA studies of complex pharmaceutical processes is justified by the substantial improvement potential towards greener processing in this sector. Although the application of LCA metrics is still not a widespread practice in the pharmaceutical industry, its use is more common today than a decade ago in order to, e.g., compare different chemical routes, assess and select materials or to perform holistic LCAs of products (see also examples collected by Jiménez-González and Overcash).116
Fig. 19 summarises possibilities and limitations of LCA in the context of engineered nanomaterials.123 Whereas data on material and energy input of engineered nanomaterials, e.g., carbon nanotubes, carbon nanofibers, nanosilver or nanoscale silica are well covered and also well reported in publications, there is only a partial or no data coverage or information regarding output related data, e.g., emissions to air, water and soil,118 often hindering a holistic LCA covering all life cycle stages.
|Fig. 19 Limitations of LCA of engineered nanomaterials, according to Miseljic et al.123 with kind permission from Springer Science and Business Media.
Hischier et al. further pointed out that in many case studies the use phase of engineered nanomaterials is claimed as the "stationary phase", i.e., having no influence on the material or energy consumption in this stage.118 Though, these life cycle stages can have a significant effect on the overall environmental performance as shown above. As an example, Hischier et al. compared the difference in the CED value of carbon nanofibers, polypropylene and steel during material production, composite production and use phase in cars, thus performing a comparison based on functionality issues. The data basis were life cycle studies performed by Khanna and his co-workers, dealing with the life cycle energy consumption and environmental impact from carbon nanofiber and carbon nanofiber composites production as a possible replacement for steel in automobile body panels.124,125 From a material and composite production point of view, the LCA results indicated (partially significantly) higher life cycle energy intensities and environmental impacts of carbon nanofibers compared to conventional materials such as aluminium and steel. This assessment was based on a kilogram scale (see Fig. 20).124 However, by substituting steel by nanocomposite materials in the automobile body panels, the environmental burdens resulting from upstream processes can be significantly reduced due to, e.g., weight reduction, and thus reduced fossil energy consumption.125
|Fig. 20 Difference in the CED value for material production, composite production and use in cars: carbon nanofiber, polypropylene compared to steel according to Hischier et al.118 using data from ref. 124, 125 reprinted with permission from Elsevier.
Thus, it is of high importance to evaluate nanomaterials in the context of their entire life cycle (cradle-to-grave LCA) including production, application, (recycling) and disposal in order to quantify their benefits versus environmental impacts in a profound comparison against conventional alternative materials.
Despite the supporting function of LCA also in chemical waste treatment, there are also some drawbacks and challenges to be handled in the future. Corominas et al.126 emphasised the need to develop standardised guidelines to ensure the quality of the LCA methodology application. In addition, the impact assessment methods need to be extended by further human and ecosystem health indicators to avoid problem shifting. Specific materials such as pathogens, pharmaceuticals or nanomaterials have not been integrated in databases yet. Thus, LCA methodologies need to be adapted to these new compounds, and ideally combined with tools like chemical and microbial risk analyses to provide a holistic analysis and decision-making for stakeholders in this sector.126,132
Depending on the specific questions to be answered by the analysis, different life-cycle approaches (ranging from gate-to-gate to cradle-to-crave) and impact assessment methods were applied. Independent of the LCA software tool, the ecoinvent database6 was used in most case studies to model LCI data of up- and downstream processes caused by the chemical synthesis under investigation. CML 2002 was found to be the most preferential LCIA method among the users in green chemical process design, whereas the follow-up method ReCiPe was applied so far only in a few studies. The use of this method in future studies is highly recommended (in combination with the latest ecoinvent dataset) in order to improve the actuality, comparability and consistency of LCA studies. The assessment of energy-intensive chemical processes further strongly benefits from the consideration of energy-related impact categories such as CEENE.
However, besides promising opportunities for LCA studies to support green chemical designs, there are also several challenges to be coped with in the future: standardised guidelines on the dependency of the specific research field need to be developed in order to ensure the quality of the LCA methodology application.133
Especially against the background of new emerging technologies such as nanotechnology, more LCI data are required that allow one to consider the whole life cycle. LCIA assessment has to be extended by impact factors for a wider range of chemical and pharmaceutical compounds. Furthermore, only a few studies reported about sensitivity and/or uncertainty analyses or disclosed the quality of their database. Thus, standardised methods for data gap or uncertainty handling as well as common rules for sensitivity analyses are urgently required. Those measures would significantly improve the comparability and reliability of the wide range of studies dealing with chemical product or process design and implementation.
|Active pharmaceutical ingredient
|Climate change
|Cumulative energy demand
|Cumulative exergy demand
|Cumulative exergy extraction from the natural environment
|Institute of Environmental Sciences, University of Leiden, The Netherlands
|Environmental, health and safety
|Global warming potential
|Human toxicity potential
|Intergovernmental Panel on Climate Change
|Life cycle inventory
|Life cycle impact assessment
|Life cycle assessment
|Life cycle costing
|Multi-criteria decision making
|Multi-objective optimisation
|Multi-walled carbon nanotubes
|Net present value
|Process intensification
|Research and development
|Simplified life cycle assessment
|This journal is © The Royal Society of Chemistry 2015


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Are you ready for spring cleaning? Get your carpet and rugs spotless by getting in touch with the best carpet cleaning services in Onkaparinga
A clean house is essential for a good and healthy daily life at home. We know that sometimes it can be complicated and tedious to follow a cleaning schedule because we all get home tired after work. Hiring professional cleaners is a good solution, either weekly or once in a while. However, not every housekeeper knows how to clean carpet properly and get it cleaned often is essential.
Luckily, there are plenty of carpet cleaning services in Onkaparinga keen to provide you with the best floor carpets and rugs cleaning. Furthermore, the cleaning company may also offer upholstery cleaning services.
Whether you need home carpet cleaning or commercial carpet cleaning, get to know the best cleaning services in Onkaparinga thanks to the Infoisinfo directory.
Why should I clean my carpet more often?
- Because you want your carpet to look clean. Moreover, the house will never look clean if the carpet doesn't.
- Because many sorts of dirt attracted by the carpet can lead to a bad smell.
- Because if you don't clean it often, stains may become permanent.
- Because you will save money. Carpets and rugs are expensive. It is cheaper cleaning than replacing.
- Because a carpet that is dirty is a source of air pollutants. Getting the carpet cleaned is essential for your health and vacuuming it yourself is not enough since bacteria will be all around the air. Count on professionals.
- Because you want to avoid mite infestations.
- Because you don't want mold to grow in your home.
How to find the best carpet cleaning services in Onkaparinga
At Infoisinfo we always work hard to be able to offer you the most useful information so that you can easily find the best products and services for you and your company in Onkaparinga. We care about you and your property and we would like to help you to make of it a nice and healthy space. For this reason, whether you need to find domestic or industrial cleaning services, we would like to give you a hand with the carpet by providing you with a list of the best carpet cleaning services in Onkaparinga.
Get in touch thanks to the contact details available like phone numbers, websites, opening times and address. In addition, you can have a look at comments and valuations from other clients about each cleaning service.
Filter by suburb
- Aldinga Beach (1)
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Carpet Cleaning Service - Onkaparinga
1 - Adelaide Cleaning Contractors - Onkaparinga
Po Box 1231, Aldinga Beach. Onkaparinga. SA, 5173.
Adelaide cleaning contractors would simply love to clean your office, child care centre, shopping, factory unit or investment property. No job is too big or small for us. We have…
2 - A & D Carpet Clean - Onkaparinga
2/22 O'Sullivan Beach Rd,Lonsdale, SA, 5160, Lonsdale. Onkaparinga. SA.
3 - Festival City Carpet Cleaning Services - Onkaparinga
By Appointment, Happy Valley,SA, 5159, Happy Valley. Onkaparinga. SA.

subset: commoncrawl


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Killswitch Engage
Killswitch Engage have announced that Light the Torch will serve as the opening act on their upcoming Spring 2020 headline tour. As fans are more than well aware, Light the Torch features front-man Howard Jones, who served as KsE's singer from 2002 through 2012.Read More
Blaze of Perdition
On February 14th, Blaze of Perdition will release their new album, 'The Harrowing of Hearts', via Metal Blade Records. For a preview of 'The Harrowing of Hearts', the video for the first single, 'Transmutation Of Sins' can be heard at: metalblade.com/blazeofperditionRead More
Cattle Decapitation
Shot during summer and fall 2019, the 'The Unerasable Past' music video showcases the striking universe of Wes Benscoter's art in conjunction with the concepts brought into play by Cattle Decapitation in stunning 4K glory. Watch now at youtu.be/MmYcFP1vTdkRead More
King Diamond
As previously announced, King Diamond has revealed the title and theme for the first studio album in 12 years: 'The Institute'! For a preview of this upcoming record, the new single, 'Masquerade of Madness', has been launched todayRead More
New Releases
New Releases
Latest News
CANCER BATS "Bat Sabbath – Bastard of Reality" EP is available on-line now!
- February 12th, 2013 – "Dead Set On Living" also available...Read More
Metal Blade Records declares Trenton Titans the official hockey team of metal
- February 11th, 2013 – Los Angeles-based Metal Blade Records, who...Read More
Swedish Death Metallers ENTRAILS finish recordings on new album and announce album title and release date!
- February 11th, 2013 – Swedish death act, ENTRAILS, have completed the...Read More
RAVEN BLACK NIGHT stream third single 'Fallen Angel' exclusively via Stormbringer.at online mag!
- February 11th, 2013 – Australian epic Heavy Metal warlords RAVEN...Read More
CATTLE DECAPITATION direct support to CRYPTOPSY's European tour this spring!
- February 11th, 2013 – CATTLE DECAPITATION will return to Europe in...Read More
NEAERA release 'Decolonize The Mind' performance video exclusively via Metal Hammer Germany!
- February 11th, 2013 – "Ours is the Storm" to be released...Read More
Shai Hulud launches third single from "Reach Beyond the Sun"
- February 11th, 2013 – East coast US shows scheduled for this week;...Read More
SIX FEET UNDER announce new album, "Unborn"; to be released March 19th
- February 11th, 2013 – Lyric video for "Zombie Blood...Read More


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Search found 47 matches. Go to advanced search
... discount, its another 15% off. So I paid $8.50 for 2. Got these in Ottawa, but they should be chain wide. https://www.lowes.ca/product/small-parts-organizers/craftsman-plastic-organizer-2-pack-997961
Went to Dollarama at Shawville (Calgary) and saw this nifty Tartan +Twine purse organizer. Googled it and it's being sold at Ulta (US website) although they don't carry the exact thing, for price reference the basic clear organizer is $23. The one at Dollarama is ...
Nov 10th, 2019 5:22 pm
Been following some of the Home Depot Milwaukee related deals; figure that this is of use for some of you? This parts organizer is fairly highly rated and recommended in the online realm. Also, I suppose one could get extra discounts from HD ? I haven't seen PACKOUT stuff with "50%" ...
Oct 21st, 2019 8:37 pm
Kids' toy storage organizer with removable plastic bins Composite wood frame with 25 lb capacity, reinforced with steel dowels White painted exterior with dark pink, light pink, light purple, and light green bins Provides easy access ...
Sep 18th, 2019 2:06 am
Amazon has AmazonBasics Mesh Desk Organizer with 25% OFF. Original price is $11.69 but after 25% OFF, price is $8.77 . Amazon's choice product. https://images-na.ssl-images-amazon.com/images/I/71oTC4Z90gL._SX679_.jpg
Aug 22nd, 2019 11:12 pm
For those interested Amazon CA has CO-Z 12 Slot Leather Sunglasses Display Case Storage Organizer for $27.99 after using discount code 3I8S99JL at checkout. This Sunglasses Organizer is made of moisture-proof PU leather. You can use it to store eyewear, jewelry, ties, ...
Aug 17th, 2019 1:19 am
Stayhold STA-30022-AMS Gray Sidekick Cargo Grips Carpets and Rubber Liners | Car Trunk Organizer | for Auto, SUV, Minivan & Boats Amazon Reference Link . $22 USD These works great. I was driving around with a box full with bottle water and it stayed in place. It's ...
Jul 20th, 2019 12:23 am
I've been looking for a cord organizer for my home office and noticed this one was $6 off (30% off) with coupon code 8NZB447X , bringing it down to $13.99. Reviews look good and it's actually cheaper than comparable cord boxes I've seen ...
Jul 10th, 2019 8:58 pm
Looking for something under $60 similar to ikea kallax shelves and I'm also open to 8-cube /12-cube or 16-cube Thanks in advance!
Feb 28th, 2019 11:33 pm
Hi Everyone, I just purchased this jewelery box as a christmas present for my wife and with the DUO deal it drops to $29.99 from $49.99. I think its a great deal and i've been happy with the quality of merchandise from Living.ca and the Primecables sites so if anyone wants to hop on board and share ...
Dec 12th, 2018 10:44 am
Got 50% off + additional $5. Looks like a decent knife organizer.
Nov 14th, 2018 1:33 pm
Prizes: 20x Side Winders ($33.99USD MSRP Each) Enter: https://www.macrumors.com/2018/10/26/macrumors-giveaway-sidewinder-cable-organizer/ Rules: Due to the complexities of international laws regarding giveaways, only U.S. residents who are 18 years or older and Canadian residents (excluding ...
Oct 29th, 2018 11:10 am
saw this in the local home depot. (Airport Road in Brampton) This is link to one box, couldn't find 3pk on the website
Oct 20th, 2018 1:30 pm
Please duo with me:https://www.living.ca/share/duodeal/jE2-3_VaslEo6owR-M_l4w?utm_source=link&utm_campaign=duo_deal
Sep 14th, 2018 2:18 am
My duodeal link: https://www.living.ca/share/duodeal/Omxwo3C_lmfUEChe1_lWuw?utm_source=link&utm_campaign=duo_deal
Aug 17th, 2018 10:59 am


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September 23, 2019
This weekend...
The last Round of the Dirt Track Lelystad Flat Track Series is gonna be the real deal! On Saturday evening we have a BBQ with a live band and on Sunday we salute the first champions of the DTL Series while enjoying a...
June 15, 2019
More Euro Flat Track! This time in the Netherlands.
Due to the overwhelming positive response to Hells Race we are now organizing a series of three weekends at Dirt Rrack Lelystad so you can keep your racing blood pumping.
May 4, 2019
Kicks off this weekend at Dirt Track Lelystad!
January 1, 2019
Around this time of year, for the last few years, I've written a fairly self-congratulatory post listing what Sideburn has done in the past year. This December I couldn't muster the same enthusiasm for a similar post, but not throu...
October 30, 2018
Indian continue to support top-level and grassroots flat track and have announced they are sponsoring one of our favourite ovals, Dirt Track Lelystad in the Netherlands. This is from the press release...
Lynda Provoost, Marketing ma...
May 18, 2018
Sideburn asked filmmaker James Cox to shoot Sideburn Hooligan racer Grant Martin at Hells Race, then explain his concept. This is what he said. it'll strike a chord with anyone who has raced motorcycles...
'Having shot a good numb...
May 16, 2018
Photo: Ian Osborne. DTRA
The only DTRA round to run at Hells Race was the Indian-sponsored Hooligan race. Having missed King's Lynn, because of a long-booked family holiday, it was my first hooligan race of the season, and boy have...
I loved Hells Race in 2017, helped by good weather and a fun road trip with Anthony and Anna from the DTRA. Just about everyone who went last year loved it, word spread and twice as many people entered for 2018, riders coming from...
March 2, 2018
Our Belgian friends are once again working with our Dutch friends again to promote the third annual Hells Race, the second at Speedway Lelystad, near Amsterdam. I went last year and had a great time.
Practice Saturday, race Sunday....
September 25, 2017
Blogs, remember them? Man, I miss the heyday of blogs. Instagram and facebook gone done killed most of them, but not all. We're still going at it, hammer and tongs, and Lennard Schuurman's Bubble Visor blog is still serving up doze...
Instagram feed


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Fatburncafe needed a new postcard, flyer or print design and created a contest on 99designs.
A winner was selected from 55 designs submitted by 15 freelance designers.
Fatburncafe Online Personal Training
we offer training programs that show people how to build muscle, burn fat and get a leaner body with minimum equipment necessary
I need an eye catching postcard that matches the website logo.
The concept I need is:
1) there are 15-20 questions written on the postcard in various sizes, fonts and color. each question is one that the average person often asks themselves or a trainer when it comes to starting an exercise program (I will provide the questions)
2) somewhere on the card I would like to have one eye catching question to grab attention. something like "Need Help?" or "20 Questions" or "Frustrated?"
3) at the bottom of the card in the area where contact info/website url will be, I would like to have written "Visitors get answers." and near/below that write "Members get results."
I want the questions to be the main focus of the card, but not too overpowering. It would be great to have a fitness related image subdued in the background as well.
***please use photo image attached in place of stock images. feel free to crop/darken/zoom or whatever you need to do in order to provide the desired effect so it matches your design. also add contact info as follows: (email) firstname.lastname@example.com (website) http://fatburncafe.com/


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Reasons Why Kitchen Remodelers Promises the Best
For most homes, guests are entertained in the kitchen and that is why we need to ensure that it is spacious and attractive. When on a mission to realize such, hiring professionals in Redding kitchen remodeling is commendable. Also, these experts come into play as they will do everything that you want them to do. To discover more about reasons why remodelers promise the best, continue here now.
They ensure proper planning and flow of activities. Since they have been involved in similar projects in the past, they know which activities need to follow the other. It is during this phase that professionals will identify remodeling works and identify those responsible. Also, planning here involves setting up dates for the kitchen remodeling works to ensure that there is no time wastage. When you rely on professionals for Chico kitchen remodeling, there is an assurance that your remodeling results will be seen soon.
Remodelers do everything as per the request of the owners. It is during the consultations that these professionals will listen to your demands and tell you if they can help deliver your goals or not. Such a move is welcomed as it ensures that they take only those remodeling works that they have skills in handling. Their long years experiences come into play in the matter as there is no type of remodeling task they can't handle.
Involvement and exposure of experts in remodeling trends gives them a better hand. No doubt, new features in remodeling are released from time to time. Since some of these contractors attend training and workshops ensuring that they have unlimited exposure to all these. For this reason, we expect them to guide on some of the best trends to use in our project.
These contractors deal in full-services. We all know remodeling can be a number of tasks and those handling such needs to be competent in the matter. Some of these tasks involve cabinetry, electrical wiring plumbing as well as flooring. Homeowners are assured of the best results since these remodelers can access all these functions with ease.
Finally, these experts have easy access to remodeling supplies. We all know that this is one of the elements that affects the flow of work Since these professionals know where to get everything, meeting goal is not a hassle. On the other hand, the remodeler you choose in this line can make or break the deal and that is why you need to be careful.


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General Auto Scaling Concepts
handle the load for your application
instance type, AMI, key pair and security groups
A launch configuration:
use that with your auto scaling groups
You can add a running instance to an ASG if the following conditions are met:
The scaling options define the triggers and when instances should be provisioned/de-provisioned
There are four scaling options:
The following table describes the scaling options available and when to use them:
The scaling options are configured through Scaling Policies which determines when, if, and how the ASG scales and
The following table describes the scaling policy options available and when to use them (and more detail further down
the page):
The diagram below depicts an Auto Scaling group with a Scaling policy set to a minimum size of 1 instance, a desired
capacity of 2 instances, and a maximum size of 4 instances:
You can define Instance Protection which stops Auto Scaling from scaling in and terminating the instances
If Auto Scaling fails to launch instances in an AZ it will try other AZs until successful
The default health check grace period is 300 seconds
Scale-out is the process in which EC2 instances are launched by the scaling policy
Scale-in is the process in which EC2 instances are terminated by the scaling policy
It is recommended to create a scale-in event for each scale-out event created
Auto Scaling can perform rebalancing when it finds that the number of instances across AZs is not balanced
Auto Scaling rebalances by launching new EC2 instances in the AZs that have fewer instances first, only then will it start
terminating instances in AZs that had more instances
Auto Scaling may go over the maximum number of instances by 10% temporarily for the purposes of rebalancing
An imbalance may occur due to:
Health checks:
terminating instances
check (300 seconds by default)
If using an ELB it is best to enable ELB health checks as otherwise EC2 status checks may show an instance as being
healthy that the ELB has determined is unhealthy. In this case the instance will be removed from service by the ELB but
will not be terminated by Auto Scaling
Elastic IPs and EBS volumes are detached from terminated instances and will need to be manually reattached
Using custom health checks a CLI command can be issued to set the instance's status to unhealthy, e.g.:
aws autoscaling set–instance-health –instance-id i-123abc45d –health-status Unhealthy
Once in a terminating state an EC2 instance cannot be put back into service again
However there is a short time period in which a CLI command can be run to change an instance to healthy
Unlike AZ rebalancing, termination of unhealthy instances happens first, then Auto Scaling attempts to launch new
instances to replace terminated instances
You can manually remove (detach) instances from an ASG using the AWS Console or CLI
When detaching an instance you can optionally decrement the ASG's desired capacity (so it doesn't launch another
An instance can be attached to one ASG at a time
You can suspend and then resume one or more of the scaling processes for your Auto Scaling group
Suspending scaling processes can be useful when you want to investigate a configuration problem or other issue with
your web application and then make changes to your application, without invoking the scaling processes
You can manually move an instance from an ASG and put it in the standby state
Instances in standby state are still managed by Auto Scaling, are charged as normal, and do not count towards available
EC2 instance for workload/application use
Auto scaling does not perform health checks on instances in the standby state
Standby state can be used for performing updates/changes/troubleshooting etc. without health checks being performed
or replacement instances being launched
When you delete an ASG the instances will be terminated
You can choose to use Spot instances in launch configurations and specify a bid price
Auto Scaling treats spot instances the same as on-demand instances
You cannot mix Spot instances with on-demand
If you want to change the bid price you need to create a new launch configuration
Auto Scaling can be configured to send an SNS email when:
Merging ASGs
Cooldown Period:
launch or terminate additional instances before the previous scaling activity takes effect
Management Console, the create-auto-scaling-group command (AWS CLI), or the CreateAutoScalingGroup API
Scaling Policies
An ASG can have multiple policies attached to it at any time
Simple scaling:
The following diagram shows a simple scaling policy:
Step scaling:
The warm-up period is the period of time in which a newly created EC2 instance launched by ASG using step scaling is
not considered toward the ASG metrics
For simple or step scaling a scaling adjustment cannot change the capacity of the group above the maximum group size or below the minimum group size
Target scaling is new and attempts to keep the utilization of instances at a target level based on CPU/memory/network etc.
Basic monitoring sends EC2 metrics to CloudWatch about ASG instances every 5 minutes
Detailed can be enabled and sends metrics every 1 minute (chargeable)
When the launch configuration is created from the CLI detailed monitoring of EC2 instances is enabled by default
When you enable Auto Scaling group metrics, Auto Scaling sends sampled data to CloudWatch every minute
Configure ASG and EC2 monitoring options so they use the same time period, e.g. detailed monitoring (EC2) and 60 seconds (ASG), or basic monitoring (EC2) and 300 seconds (ASG)


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13 results for "Freely available, KB reading room only, Book studies, Manuscripts, Bibliographies, Catalogues"
Alba amicorum voor 1800
Catalogue of the alba amicorum (to 1800) in private or public collections in the Netherlands, including provenance and reference literature.
Belgische Bibliografie (BB)
Official Belgian Bibliography; publications from and about Belgium; instalments of the last 12 months
Book Sales Catalogues of the Dutch Republic 1599-1800
Bibliography of Dutch book auction and stock catalogues, price lists if available. Scans from some catalogues can be seen in Book Sales Catalogues Online.
Conservering: documentatie
Bibliography; conservation; restauration; preservation; materials; methodology; techniques; damage profiles; archives, libraries; digital preservation
Handschriften KB: documentatie
Literature on manuscripts in the collections of the Koninklijke Bibliotheek and Museum Meermanno..
Karlsruher Virtueller Katalog
Integrated search engine for research library catalogues in German speaking countries, national libraries worldwide & commercial vendors.
Medieval Illuminated Manuscripts (MIM)
Miniatures from medieval manuscripts of the Royal Library and Museum Meermanno.
Medieval Manuscripts in Dutch Collections (MMDC)
Medieval manuscripts in public collections in the Netherlands.
National Dutch research portal: academic publications (theses/reports, articles), data sets, research projects and organisations.
Nederlandse Bibliografie
Official Dutch bibliography, publications from or about the Netherlands or the Dutch language; includes announced publications