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Article
Techno-Economic Analysis of a Glycerol Biorefinery
Sebastiano D'Angelo, Agostino Dall'Ara, Cecilia Mondelli,
Javier Pérez-Ramírez, and Stavros Papadokonstantakis
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.8b03770 • Publication Date (Web): 26 Oct 2018
Downloaded from http://pubs.acs.org on October 28, 2018
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Page 1 of 39 ACS Sustainable Chemistry & Engineering
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Techno-Economic Analysis of a Glycerol
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Biorefinery
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16 Sebastiano C. D’Angelo,† Agostino Dall’Ara,† Cecilia Mondelli,*,† Javier Pérez-Ramírez*,†
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19 Stavros Papadokonstantakis*,‡
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†Institute for Chemical and Bioengineering, Department of Chemistry and Applied Biosciences,
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23 ETH Zurich, Vladimir-Prelog-Weg 1, 8093 Zurich, Switzerland.
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25 ‡Division
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of Energy Technology, Department of Space, Earth and Environment, Chalmers
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28 University of Technology, Hörsalsvägen 7B, 41296 Gothenburg, Sweden.
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31 *Corresponding authors. Cecilia Mondelli: cecilia.mondelli@chem.ethz.ch
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33 Javier Pérez-Ramírez: jpr@chem.ethz.ch
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Stavros Papadokonstantakis: stavros.papadokonstantakis@chalmers.se
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ACS Sustainable Chemistry & Engineering Page 2 of 39
1
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3 ABSTRACT
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6 Biodiesel is an environmentally-friendly alternative to fossil fuels, which is experiencing a
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8 steep growth in market size. Since the most common biodiesel production technology is based on
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10 the transesterification of triglycerides, a burgeoning amount of glycerol byproduct is obtained. In
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order to address this economic and ecologic drawback, several chemocatalytic technologies have
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15 been developed to exploit this compound to feed the market with added-value products. Lactic
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17 acid, acrylic acid, allyl alcohol, propanediols, and glycerol carbonate have emerged as the most
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relevant candidates for this purpose. In previous studies, an environmental and economic
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22 assessment of a glycerol biorefinery built on these valorization pathways has been performed,
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24 taking into account only the operating costs in relation to the economic aspects. This study
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26 evaluates for the first time the investment required by these glycerol valorization processes, based
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29 on the Guthrie, Taylor, and Aspen capital cost estimation methods, and then assesses the potential
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31 of a heat-integrated glycerol biorefinery. Glycerol carbonate stands out as the dominant product to
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33 maximize the profitability with respect to the glycerol utilized, while 1,2-propanediol and allyl
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alcohol are determined as target compounds to be included in the glycerol biorefinery product mix
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38 if further reductions of the environmental impact are sought after. This early-stage techno-
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40 economic analysis provides a sounder basis toward the practical realization of an integrated facility
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sustainably upgrading waste streams from the processing of renewables into commodities, thus
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45 promoting the concept of circular economy.
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49 KEYWORDS: Chemocatalytic glycerol valorization, capital cost, early-stage relative costing,
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52 integrated biorefinery, renewables
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1
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3 INTRODUCTION
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6 In response to the commitments initiated by the Group of Twenty (G20) in 2009 and subscribed
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8 by 2016 by more than 50 countries to phase out fossil-fuel subsidies,1 the amount of biofuels
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10 marketed has experienced a dramatic increase in the last decade. In particular, the quantity of
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biodiesel is expected to further raise by 5 billion liters, reaching a total of ca. 40 billion liters by
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15 2027, thanks to favorable governmental policies in Brazil, Argentina, Indonesia, and other
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17 developing countries.2 Since transesterification of triglycerides is the most industrially practiced
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method to attain this fuel owing to the comparable properties of the product to fossil-derived
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22 diesel,3 the amount of glycerol attained as a by-product of this reaction in a 1:10 weight ratio with
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24 biodiesel has for long exceeded the commercial demand for this chemical in the cosmetic,
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26 pharmaceutical, and food industries. Although the utilization of first-generation vegetable oils as
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29 feedstock is expected to decrease substantially, non-edible oils and waste animal fats are
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31 considered as promising alternatives and waste oils are already being collected and successfully
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33 exploited for the same purpose.2,4 Specifically, it is foreseen that 50 Mt y−1 biodiesel will be
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produced from these sources, implying an even greater availability of the triol in the future.5
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38 As the most prominent example of the efforts directed to the valorization of side streams in
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40 biomass upgrading, the sustainable conversion of glycerol to higher added-value products has been
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widely investigated in order to lower the environmental impact of biodiesel production and to raise
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45 its profit to comparable levels with respect to the fossil-derived counterpart.6-11 In this context, the
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47 concept of a glycerol biorefinery producing commodity chemicals, polymer precursors, and
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49 solvents (i.e., lactic and acrylic acids, glycerol carbonate, propanediols, epichlorohydrin, and allyl
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52 alcohol), has been recently proposed (Error! Reference source not found.).12 The portfolio of
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54 products was selected based on their commercial value, the similar size of their markets to that of
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1
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3 the feedstock, as well as the fact that their preparation, mediated by state-of-the-art catalytic
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6 technologies, is generally associated with a high atom economy, since the original C3 backbone
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8 and a high degree of functionalization are retained. Through rigorous process modeling and life-
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10 cycle analysis considering materials, energy, and waste treatment, a generally milder
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environmental impact was determined for the glycerol-based routes compared to the corresponding
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15 conventionally applied technologies.12 More importantly, it was demonstrated that a heat-
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17 integrated network of processes mimicking a multiproduct biorefinery13 paves the way to a lower
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ecologic footprint with respect to the single production lines and to additional economic
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22 advantages from the operating cost standpoint.
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24 To achieve a more reliable techno-economic analysis, a further aspect that should be addressed
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26 is the capital cost,14 which may weigh to a substantial extent in the overall assessment of profit
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29 and greenness. As biorefineries are considered as pioneering plants built with forefront
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31 technologies, a high degree of uncertainty is associated with this kind of computations, limiting
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33 the accuracy of early-stage studies to the order-of-magnitude level.15 This does not only depend
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on the assumptions of the model applied but also on the possible lack of information on process
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38 considerations, such as equipment cost or process development scale. Hence, an accurate capital
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40 expenditure estimation is essential to evaluate the feasibility of a project.16 Still, while this is to be
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fulfilled for a well-developed plan, a trade-off between accuracy and time is widely accepted for
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45 an emerging scenario, for which comparing multiple alternative configurations might be
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47 significant already from early stages of process design. In the latter situation, the techno-economic
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49 analysis primarily aims at relatively costing the different options. Following this ranking, further
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52 efforts will be dedicated to gather a more realistic picture of the leads toward detailed process
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54 design, upstream and downstream logistics (e.g., optimal plant capacity with respect to
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1
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3 geographical location and supply chain optimization, considering also uncertainties in local and
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6 global market conditions and perspectives),17,18 eventually obtaining a precise estimation of their
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8 costs.19
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10 Herein, we quantify the weight of total investment costs on the total profit for the glycerol
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upgrading paths previously studied, investigating at first the single production lines through three
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15 costing methods and then tackling the integrated facility. With respect to the glycerol biorefinery,
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17 an optimization of the feed distribution among the different routes in order to achieve the best
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profit or the best compromise between economic and environmental parameters is carried out.
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22 Given the low technology readiness level (TRL) of most of the processes evaluated, this study can
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24 be considered as the first complete early-stage economic assessment for this kind of biorefinery
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26 valorizing waste from biomass upgrading processes. Thus, it stands as a valuable starting point to
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29 investigate promising plant options at a more detailed design level up to large-scale
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31 implementation and sparks interest in a broader application of economic and environmental
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33 process analysis to other emerging renewable technologies to support the realization of a circular
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economy.
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40 METHODS
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Process flowsheets, operating costs, and environmental life-cycle impact assessment. The
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45 process models and flowsheets for the various glycerol-to-chemicals paths presented in Figure 1
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47 have been discussed in detail in previous publications of some of the authors.12,20,21 Herein, these
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49 will be referred to as the manufacture of lactic acid via dihydroxyacetone (P1), lactic acid via
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52 pyruvaldehyde (P2), acrylic acid (P3), allyl alcohol (P4), 1,2-propanediol (P5), 1,3-propanediol
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54 (P6), and glycerol carbonate (P7). In these studies, multiple plant configurations have been
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1
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3 considered for the production of each chemical to identify promising process layouts in terms of
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6 operating costs and cradle-to-gate life-cycle impact assessment. Three life-cycle impact
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8 assessment metrics have been applied: the cumulative energy demand (CED), the global warming
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10 potential (GWP), and the Eco-indicator 99 (EI99). These metrics have widely been used in life-
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cycle analysis (LCA) studies.22-26 While CED and GWP are LCA metrics directly or indirectly
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15 associated with energy and greenhouse-gas emissions, they also cover resource-related aspects.27
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17 EI99, on the other hand, relates to a wider spectrum of aspects and has been used as an aggregated
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index (i.e., in the hierarchist weighting approach) to identify the extent to which a multicriteria
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22 assessment would result in different conclusions toward optimal process layouts. In the majority
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24 of the cases, common trends between these LCA metrics have been identified. All background
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26 data for the operating costs and cradle-to-gate environmental assessment metrics have been
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29 presented in the aforementioned studies.12,20,21 The life-cycle impact of building the glycerol
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31 biorefinery plant has not been considered in these studies and is also not part of this work.
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33 It should be noted that the process flowsheets contained rigorous models developed in the
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software Aspen Plus® (versions 8.6 and 8.8). However, the process flowsheets did not undergo a
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38 rigorous structural and parametric optimization. This means, for instance, that in terms of
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40 separation trains, recycling of water, chemicals, and other auxiliaries as well as operating
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parameters of the respective process operations, a series of sensitivity analysis tests were
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45 conducted to attain preferable process layouts. In this procedure, reactors have been simulated
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47 under the assumption that the catalyst performance observed at the laboratory scale remains
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49 unaltered at larger scales, while aspects related to process simplicity and heuristics for setting the
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52 operating parameters of the downstream separation section have been considered to safeguard
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54 from complex process structures, unrealistic process equipment dimensions, and, at the same time,
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1
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3 to qualitatively account for capital and operating costs trade-offs (e.g., the reflux ratio for
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6 distillation columns was typically set in the range of 1.2−1.5 times the theoretically minimum
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8 reflux ratio, the columns slenderness ratio were mostly kept between 5−30, etc.). Moreover, heat
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10 integration of the process flowsheets has been conducted in terms of targeting the minimum energy
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consumption using pinch analysis. Rigorous heat exchanger network design, utility targeting, or
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15 total site analysis approaches have not been considered in earlier studies,12,20,21 as the focus was
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17 on the identification of the most promising chemical paths for glycerol valorization and the
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interplay between lab experiments, process synthesis, and sustainability assessment. Thus, it is
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22 likely that the process flowsheets of the most promising process options discussed in this work can
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24 undergo further optimization at later stages of process design. Nevertheless, considering the
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26 hierarchical paradigm for process design generally accepted over the last few decades,28,29 they are
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29 satisfactorily comprehensive to cover the scope of early-stage relative costing and sustainability
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31 assessment. In this work, only one process layout was selected for further assessment of the capital
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33 cost for each glycerol upgrading route, based on the best results reported elsewhere.12,20,21 A
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summary of the most important information about these process flowsheets is provided in the
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38 Supporting Information (SI).
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40 Capital cost estimation methods for early process design stages. Capital cost (or investment
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cost) estimation is an important factor to determine the feasibility of a project and is assessed at
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45 all levels during the front-end loading process (FEL), i.e., the conceptual development of a project
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47 in process industry. It is possible to distinguish between two major categories of cost estimation:
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49 grassroots and battery limits. Grassroots relate to an estimation of the entire plant, including field
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52 preparation, buildings, processing facilities, utilities, services, and storage. Battery limits can be
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54 divided into inside battery limits (ISBL), which include cost estimations of the bare processing
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1
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3 facilities, and outside battery limits (OSBL), which comprise all the rest of the direct capital cost,
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6 (i.e., the cost related to utilities, storage, waste treatment, and land management). The direct capital
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8 cost is then defined as the sum of ISBL and OSBL, while the indirect capital cost refers to the
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10 engineering, construction, and contractor expenses. The sum of direct and indirect capital cost is
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named fixed capital investment. Besides direct and indirect capital costs, two additional relevant
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15 factors which are accounted in total investment cost estimation are working capital and start-up
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17 expenses. The first is the amount of money necessary to pay operating expenses, raw materials
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purchase, accounts receivable/payable, and taxes payable. The second includes the funds allocated
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22 for the cost of employee training and equipment adjustment at the start of the project.
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24 A universally-accepted standardized categorization of the investment cost estimates has not
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26 been developed yet. Among the most widely shared classifications, it is worth to mention that
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29 proposed by the Association of Advancement of Cost Engineering (AACE), which includes five
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31 main classes of cost estimation, three standardized Classes (Order of Magnitude, Budget, and
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33 Definitive) accepted by ANSI, a similar categorization into four Classes (Order of Magnitude,
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Study, Budget, and Definitive) elaborated by the British Association of Cost Engineers (ACostE),
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38 and the classification from the European Commission into 9 TRLs. Tsagkari et al.15 summarized
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40 these classification practices as presented in Table 1. With these premises, it is evident that capital
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cost analysis is a key factor in the development of a plant project, already from the early stages of
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45 process design. Indeed, the methodologies applied in this work refer to estimations for TRL1−4
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47 and the respective classes (Table 1).
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49 From a methodological perspective, it is possible to divide the capital cost estimation methods
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52 in three main categories: power law or exponential, factorial, and significant process step methods.
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54 The first kind of approach is widely used, since the cost data can be extrapolated from one scale
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1
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3 to another. If data from similar plants or plants with similar processes are available, these can be
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6 exploited to assess the capital costs of the project of interest. The absence of data may lead to a
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8 less reliable estimation. Unfortunately, this is the case for biorefineries, which are industrial
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10 complexes at an infancy stage, while for the few existing dedicated bio-based production lines of
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chemicals and fuels companies it is not typical to share detailed economic data on state-of-the-art
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15 or upcoming technologies. The standard form of the correlation used in this class of estimations
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17 is:
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19 p
20 C1  S1 
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   t (1)
C2  S 2 
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24 where C1 and C2 are the costs of an item with size S1 and S2, respectively, p is an exponent that
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26 varies between 0.3 and 1.2, depending on the item or the process being scaled, and t is a generic
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correction factor, used to consider the year and location of the estimation and corrected for
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31 differences in temperature, pressure, and materials of construction. A p value lower than 1
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33 indicates economy of scale (i.e., incremental costs decrease with larger capacities). A p value
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bigger than 1 usually designates that a multistreaming strategy needs to be adopted (i.e., because
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38 of limitations in the available equipment capacities).
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40 Factorial estimating, the second cost estimation approach, relies on the assumption that all
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42 categories of capital expenditure in an industrial plant depend on the cost of the purchased
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45 equipment. Accordingly, a detailed list of process equipment and its relevant cost has to be firstly
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47 estimated from literature or vendors cost catalogues before factors can be regressed and applied to
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49 predict the capital costs of a specific industrial plant. The critical point is data gathering, since the
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level of detail might not be satisfactory at early stages of process design. Because of the huge
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54 amount of information required, this class of estimates is best suited for more advanced phases of
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56 a plant project. Tsagkari et al.15 have suggested that, in the case of biorefineries, this method should
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3 be used for Class 5 estimations only if the plant of interest does not involve state-of-the-art
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6 technology, as a biodiesel production plant for instance, while it is more efficient for estimates of
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8 Classes 4 or 3.
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10 The significant process step estimation, the third cost estimation approach, calculates capital
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costs as a function of major process steps and parameters, such as throughput, temperature and
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15 pressure boundaries, and construction materials. This class of methods is usually greatly suitable
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17 for early capital cost estimations, as no detailed knowledge about the process structure or
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equipment is necessary in most cases. In spite of this, some of the models proposed over time
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22 require a significant amount of information and are not very well suited for Class 5 capital cost
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24 estimation. A relevant issue in these methods is the definition of a relevant process step, which is
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26 still matter of interpretation. ChemE and ACostE have proposed in 2000 the following general
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29 definition: ‘A functional unit is a significant step in a process and includes all equipment and
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31 ancillaries necessary for operation of that unit.’
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33 Herein, three methods have been selected for the capital cost estimation:
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- the Guthrie method ,which uses an exponential approach,30
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38 - the Taylor method, which uses a process step scoring estimation,31
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40 - the Aspen Capital Cost Estimator™ (ACCE), a commercially available tool using costing
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models subjected to copyright.
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45 These methods are further described in the SI, where also more detailed information about sizing
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47 and costing of specific process units and steps can be found.
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49 Plant profitability evaluation. The profitability assessment of the various process layouts was
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52 performed on the basis of the annualized net profit before taxes (ANP) and the payout time (PT).
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54 The total investment (TI) is equivalent to the sum of the plant cost at battery limits (fixed cost),
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3 the amount of money necessary for the first months of activity of the plant (working capital), and
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6 the startup costs. In this work, the working capital and the startup costs were assumed to be 20 and
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8 10% of the fixed costs, respectively, typical values taken from the literature.30 ANP is calculated
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10 based on eq. 2:
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12
i 1  i 
n
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14 ANP  GP  TI (2)
1  i 
n
15 1
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17 where GP stands for gross profit and is the difference between the gross sales (GS) and the products
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20 and the manufacturing costs (MC) (i.e., the costs for utilities, chemical auxiliaries, and raw
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22 materials). The index i expresses the annual growth of the assets of a company. This value usually
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24 ranges between 5 and 10%, and was assumed to be 8% in this study. Finally, n is the plant lifetime,
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which was here considered as 20 years. PT is obtained by using eq. 3:
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29 TI
PT  (3)
30 FC  SC
31 GS  D 
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n
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34 In this equation, TI and GS are as defined previously, and the term added in the denominator is the
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36 depreciation (D), here accounted for as 10% of the annualized sum of fixed and startup costs. The
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payout time can be defined as the time needed to recover the initial investment through sales.
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41 Glycerol biorefinery assessment. First, a profitability study was performed for each
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43 individual glycerol-to-chemical production line, designating the case of a dedicated monoproduct
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45 glycerol biorefinery. The plant capacity with respect to refined glycerol feedstock ranged between
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48 10−100 kt y−1. The maximum value of this range corresponds to ca. 10 times the maximum amount
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50 of glycerol produced by the ASB Biodiesel plant in Hong Kong, which came into operation in
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52 2013.32,33 Considering that a glycerol refinery plant would be best placed in the proximity of a
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biodiesel production plant to minimize glycerol transportation costs, the lower values of the
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3 glycerol feedstock range correspond to such a scenario. Higher values refer to the case of biodiesel
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6 plants of increased capacity in the future. They can also refer to a glycerol plant optimally placed
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8 to receive feedstock from more than one biodiesel plant and produce higher volumes of chemicals
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10 trading-off glycerol transportation costs and plant economy of scale. In this regard, it should also
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be taken into account that a full techno-economic study would not only consider the optimal plant
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15 placement with respect to glycerol feedstock but also the corresponding (local) market conditions
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17 in relation to the potential product or mix of products. These aspects lie outside the scope of the
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present study, which mainly focuses on a relative techno-economic comparison between the
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22 individual production lines and integrated biorefinery options.
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24 For the heat integration (energy targeting via pinch analysis), the hot utilities considered are
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26 steam at 6 bar and natural gas, and the cold utilities are cooling water (283−288 K) and NaCl brines
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29 (253−268 K). A realistic minimum temperature approach of 10 K was assumed for all of the runs.
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31 The heat integration network achieving the minimum energy targets was not designed. Instead, an
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33 estimate of the overall heat transfer area required was performed based on the concept of vertical
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heat transfer.30 The minimum number of heat exchangers as calculated by the Euler’s rule34 was
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38 used to equally divide the estimate of the overall heat transfer area to individual heat exchanger
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40 units. This approach was applied to both the heat integration of the individual production lines and
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the integrated biorefinery scenarios. In the latter case, only the non-heat integrated process layouts
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45 of the individual production lines were considered. For the integrated glycerol biorefinery, a series
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47 of optimization scenarios were performed to find the optimum production mix. The problem
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49 formulation is presented in eqs. 4−15:
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52 Max ANP  x  (4)
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s.t.
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1
2
3 7
4 ANP  ch  HU sav  cc  CU sav  Cupd,int  ANPj (5)
5 j 1
6
7
i 1  i 
n
8
9 ANPj  x j  Fg  GPj  TI j (6)
1  i 
n
10 1
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12 TI j  f j ( x j , Fg ) (7)
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15 Cupd,int  g  x , Fg  (8)
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17
18 7
19 GWP  GWPj cf h  HU sav  cf c  CU sav (9)
20 j 1
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22
23 GWPj  x j  Fg  GWPj (10)
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25 7
26 HU sav  x j  Fg  HU j  HUTk  x  (11)
27 j 1 k
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29 7
30 CU sav  x j  Fg  CU j  CUTm  x  (12)
31 j 1 m
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33
7
34
35 x
j 1
j 1 (13)
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38 x j  0,  0.1 1 (14)
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41 GWP   (15)
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In these equations, ANP is the annual net profit of the heat integrated glycerol biorefinery for a
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46 capacity of purified glycerol (Fg) equal to 100 kt y−1 in the scenarios of this study, xj is the
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48 percentage of glycerol feed used in the j production line, ANPj is the annual net profit of the j
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51 production line without heat integration at the production line level, GPj is the specific gross profit
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per kg of glycerol of the j production line without heat integration at the production line level, TIj
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56 is the total investment of the j production line excluding heat exchangers, GWP is the annual global
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1
2
3 warming potential as an LCA metric of the heat integrated biorefinery, GWPj is the annual global
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6 warming potential of the j production line without heat integration at the production line level,
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8 GWPj is the specific global warming potential per kg of glycerol of the j production line without
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10
11 heat integration at the production line level, HUsav and CUsav are the annual hot and cold utility
12
13 savings (i.e., in energy units), respectively, of the heat integrated biorefinery based on pinch
14
15
16 analysis for maximum energy recovery, Cupd,int is the updated capital cost of heat integration (i.e.,
17
18 the estimated cost of the heat exchanger network for heat integration at the biorefinery level)
19
20
21
according to the Guthrie method, HU j and CU j are the specific hot and cold utility consumptions
22
23 per kg of glycerol of the j production line without heat integration at the production line level,
24
25
26
HUTk and CUTm are the hot and cold utility targets of the pinch analysis for the k and m type of
27
28 utility respectively, ch and cc are cost coefficients for the hot and cold utility savings respectively,
29
30 and cfh and cfc are global warming potential coefficients for transforming the hot and cold utility
31
32 savings into CO2 equivalents.
33
34
35 This is a mixed integer non-linear programming (MINLP) optimization problem. The non-
36
37 linearity arises from eqs. 5−8, namely because of the non-linear dependence of TIj and Cupd,int on
38
39 x. The integer nature of the problem arises from eq. 14, where a product line either receives a
40
41
42 minimum amount of glycerol feedstock (10%) or the respective product is not produced at all. The
43
44 problem is solved based on a ‘master-subproblem’ configuration, where the master problem
45
46 optimizes the production mix and the subproblem finds the optimum energy utility targets and
47
48
49
estimates the respective capital cost of heat integration at the biorefinery level. Varying the 𝜀
50
51 constraint value, a series of optimization problems were solved to investigate the trade-off between
52
53 the economic and environmental objectives and the impact on the optimal production mix. The
54
55
solution procedure for each optimization problem is based on a combination of genetic and local
56
57
58
59
1
2
3 search algorithms utilizing a computationally efficient (for the size of this MINLP problem) multi-
4
5
6 start procedure as described in detail in the SI.
7
8
9
10 RESULTS AND DISCUSSION
11
12
13
Capital cost estimation of the single glycerol valorization processes: comparison of
14
15 methods. The capital cost analysis was performed on the single production lines based on the
16
17 Guthrie, Taylor, and ACCE methods. All the plants were scaled and investigated in order to cover
18
19
a refined glycerol feed ranging from 10 to 100 kt y−1. Heat integration at a minimum temperature
20
21
22 approach of 10 K was performed in all cases on the single lines to calculate the minimum hot and
23
24 cold utility target, and estimate the capital cost for a heat-integrated exchanger network. The results
25
26 for the glycerol paths to 1,2-propanediol and glycerol carbonate are presented in Figure 2. These
27
28
29 two production lines are discussed here in more detail, since they play an important role in the
30
31 integrated biorefinery production mix (vide infra). Similar trends were, however, observed for the
32
33 other glycerol upgrading paths, as presented in the SI.
34
35
36
Concerning the glycerol-to-1,2-propanediol route (Figure 2a), an exponential trend of the
37
38 capital costs as a function of the feed amount was observed using all three methods, with values
39
40 of the same order of magnitudes. Compared to the other glycerol valorization processes, the
41
42
similarity of the results between the methods is related to the fact that all of the units included were
43
44
45 conventional, belonging to the class of units originally specified by Guthrie,30 as well as to the
46
47 relatively low number of significant process steps with relatively low throughputs (i.e., out of 5
48
49 steps, three have values around unity, while the others are around 8, still being of a similar order
50
51
52 of magnitude).
53
54
55
56
57
58
59
1
2
3 In the case of the production of glycerol carbonate (Figure 2b), the Taylor approach provided
4
5
6 a significantly higher estimation of the costs compared to the other two methods. For the higher
7
8 capacities, it can exceed the estimation obtained through the Guthrie method by more than 250%.
9
10 This difference is related to the fact that the Taylor method heavily weighs a parameter such as the
11
12
13
throughput of most of the units, which is here quite high for units like the reactor, the flash
14
15 separator, the crystallizer, and two of the four columns present, compared to the other cases. This
16
17 is a direct consequence of the huge amount of solvent that needs to be removed, which counts
18
19
more in the Taylor method than in the other approaches.
20
21
22 As presented in greater detail in the SI, for lower plant capacities (i.e., glycerol feed of
23
24 10 kt y−1), the Taylor method generally gives significantly higher capital costs estimates (i.e.,
25
26 5−10-times higher) for the production of lactic acid via DHA, lactic acid via pyruvaldehyde,
27
28
29 acrylic acid, and glycerol carbonate. Moderately but consistently higher capital cost estimates (i.e.,
30
31 2−4-times higher) are obtained for 1,2- and 1,3-propanediols, and allyl alcohol. This discrepancy
32
33 is reduced for higher plant capacities, since the Taylor method exhibits a more pronounced trend
34
35
36
according to the economy of scale than the Guthrie and ACCE methods in the range of plant
37
38 capacities explored. In particular, for the case of lactic acid via DHA, lactic acid via PVA, acrylic
39
40 acid, and glycerol carbonate, 2−6-times higher capital cost estimates are obtained by the Taylor
41
42
method compared to the Guthrie and ACCE strategies, while capital cost estimates higher by only
43
44
45 1.5−2.5 times are determined with the Taylor method for the cases of 1,2- and 1,3-propanediols,
46
47 and allyl alcohol.
48
49 Figure 3 shows the decomposition of the total capital costs, as calculated by the Guthrie
50
51
52 method, into three main process components: the reactors, the separation columns, and auxiliary
53
54 equipment. Comparable trends are found for all plant capacities investigated. The reactors are the
55
56
57
58
59
1
2
3 most capital-intensive part of the production of the two propanediols due to the requirement for
4
5
6 gas phases and the dilution of the glycerol feedstock. The separation trains in the multi-product
7
8 allyl alcohol process, the challenging purification of glycerol carbonate, and the recovery of
9
10 unreacted pyruvaldehyde in the production of lactic acid are the reasons why the capital costs of
11
12
13
these products are dominated by the separation columns.
14
15 Regarding distillation columns, not only their number but also the allowed slenderness ratio
16
17 are important costing factors. When the latter is higher than 15, which is the case for most of the
18
19
columns in the acrylic acid via acrolein production path, the column is conceptually divided into
20
21
22 more columns in series (i.e., decreasing the length of the individual column parts) and thus the
23
24 only part of the column that is costed multiple times is the column vessel (i.e., the column still has
25
26 one reboiler and one condenser overall). However, when the slenderness ratio is less than 3, a
27
28
29 standard multi-streaming approach is used (i.e., multiple columns in parallel). Accordingly, the
30
31 column vessel as well as the condenser and the reboiler are costed multiple times, leading to higher
32
33 costs. This is frequently encountered in the lactic acid via pyruvaldehyde (P2, three out of six
34
35
36
columns), allyl alcohol (P4, two out of eight columns), and glycerol carbonate (P7, three out of
37
38 four columns) processes. It also applies to the manufacture of lactic acid via dihydroxyacetone
39
40 (P1, one out of three cases) and 1,3-propanediol (P6, one out of two columns), but it does not result
41
42
in the separation equipment dominating the equipment cost due to the lower number of columns.
43
44
45 Since the flowsheets have not been subjected to rigorous optimization for the number of stages
46
47 and reflux ratios for the various capacities tested (i.e., but only to local sensitivity analysis), these
48
49 results may be over- or underestimating the column capital costs to some extent. However, this is
50
51
52 not expected to distort the main trends observed regarding the contribution of the different
53
54 equipment classes to the overall equipment cost.
55
56
57
58
59
1
2
3 The need for pyruvaldehyde recovery is an important distinguishing factor between the two
4
5
6 routes to lactic acid (i.e., P1 and P2), which was also pointed out in terms of energy consumption
7
8 in a previous study.12 Concerning lactic acid via dihydroxyacetone, multieffect evaporation
9
10 followed by crystallization was sufficient to concentrate the dixydroxyacetone solution at the
11
12
13
output of the reactor to isolate the intermediate. This denotes a much simpler process in terms of
14
15 energy and capital investment compared to the path featuring pyruvaldehyde as the intermediate.
16
17 Tables 2 and 3 summarize economic and environmental aspects of the single production lines
18
19
with heat integration. For the energy and material costs and environmental impacts, the same
20
21
22 background data were used as in previous studies.12,20,21 For the calculation of the environmental
23
24 life-cycle impact metrics, glycerol was assumed to be a partially utilized co-product of biodiesel,
25
26 the non-utilized part of which would be treated in conventional waste treatment facilities, unless
27
28
29 otherwise utilized (i.e., this is the part utilized in glycerol-to-chemicals in the present study). Heat
30
31 integration was uniformly performed in all production lines on the basis of maximum energy
32
33 recovery via pinch analysis for a minimum temperature approach of 10 K. Compared to the earlier
34
35
36
works mentioned, more heat sources and sinks were used (e.g., distillation columns were also
37
38 included in the heat integration), which led here to lower operating costs.
39
40 The annualized capital costs in Table 3 refer to the upper limit of the purified glycerol
41
42
feedstock considered (100 kt y−1). The manufactures of allyl alcohol and 1,2-propanediol are the
43
44
45 most and least capital-intensive processes, respectively. When no capital cost is considered, the
46
47 profit margins lie in a range from 4% (lactic acid via dihydroxyacetone) to 40% (1,3-propanediol),
48
49 according to the Guthrie method. In the case of the Taylor method, these percentages are higher
50
51
52 by 1.5−6 times for the higher plant capacities, as mentioned above.
53
54
55
56
57
58
59
1
2
3 The profitability values in Table 3 indicate a profit margin ranging between 0.5−10 $ kgproduct−1
4
5
6 in all cases. It should be noted that the exceptionally high profitability per unit mass of allyl alcohol
7
8 production is mainly due to the multi-product nature of this process (e.g., acrolein and acetol are
9
10 also obtained as valuable products), as it is also indicated by the very low, negative value of the
11
12
13
operating costs in Table 2. The processes can be ranked from the most to the least profitable as
14
15 P7 > P4 > P1 > P5 > P2 > P6 > P3. If capital costs are not considered (i.e., the profit for each
16
17 production line is derived by subtracting only the operating costs from the product price, neglecting
18
19
the annualized the capital costs), the trend is P7 > P4 > P6 > P1 > P5 > P2 > P3. Accordingly, the
20
21
22 production of glycerol carbonate is the most profitable option (profit of 1.94 $ kgglycerol−1),
23
24 followed by that of allyl alcohol (profit of 1.27 $ kgglycerol−1), while acrylic acid is least favorable
25
26 (profit of 0.26 $ kgglycerol−1), in both cases. The main difference relates to the manufacture of 1,3-
27
28
29 propanediol, which is strongly penalized by its capital cost.
30
31 A comparison of our result with literature data is only possible with respect to economic
32
33 aspects, since only one study investigated life-cycle environmental impacts for two of the
34
35
36
chemicals targeted and by applying different boundary conditions and allocation approaches from
37
38 ours. Lactic acid produced via a biocatalytic method has been reported by Gargalo et al.35 to have
39
40 a cost of ca. 1.2 $ kgproduct−1. The values here obtained for the manufacture of the same chemical
41
42
via two alternative routes (P1, P2) are substantially lower (ca. 0.3−0.5 $ kg−1) due to the benefits
43
44
45 of following chemo- rather than biocatalytic paths, as thoroughly discussed in previous
46
47 studies.12,20,21 For 1,2-propanediol, a production cost of 1.4 $ kgproduct−1 has been calculated by
48
49 Gargalo et al. in the same paper,35 while Almena et al.11 refer to a production cost of
50
51
52 ca. 0.4 $ kgproduct−1. The latter value coincides with the result of our study for this compound. For
53
54 1,3-propanediol, the biocatalytic path assessed by Gargalo et al.35 leads to a cost of
55
56
57
58
59
1
2
3 ca. 2 $ kgproduct−1, which is significantly lower than the value of 3.4 $ kgproduct−1 determined here
4
5
6 for a chemocatalytic path to this chemical. This higher cost originates from the relatively low
7
8 reaction selectivity (66%), the high reactor pressure (50 bar), and the excess of hydrogen utilized.
9
10 The manufacture of glycerol carbonate and allyl alcohol from glycerol was not evaluated by other
11
12
13
authors. If other alcohols are considered, production costs in the range of 1.5−1.7 $ kgproduct−1 are
14
15 reported for the methanol, ethanol, and isobutyl alcohol,11.35 whereas a value of 3.2 $ kgproduct−1 has
16
17 been estimated for n-butanol.35 Our result for the production cost of allyl alcohol is
18
19
−7.7 $ kgproduct−1, since the advantage of co-producing acetol and 2-ethyldioxalane is fully
20
21
22 allocated to the manufacture of allyl alcohol. Finally, although acrolein did not belong to the
23
24 products targeted by this study, a parallel with literature reports can be made for this chemical,
25
26 since an acrolein solution is produced as an intermediate in the production of acrylic acid here
27
28
29 assessed. The works cited above11.35 indicate an acrolein costs of 0.8−3.1 $ kgproduct−1. Since a
30
31 manufacturing cost of acrylic acid of 1 $ kgproduct−1 was obtained in the present work, the cost of
32
33 the acrolein intermediate is expected to be close to the lower bound of the range reported in the
34
35
36
literature.
37
38 From the values reported in Table 2 for the alternative productions (mainly fossil-based) of
39
40 these chemicals, the mildest environmental impact per kg of glycerol would be associated with
41
42
glycerol carbonate production (5.8 kgCO2eq kgglycerol−1) followed by allyl alcohol manufacture
43
44
45 (5.4 kgCO2eq kgglycerol−1). Figure 4 summarizes the profitability results for all glycerol capacities. It
46
47 is evident that the trends are comparable throughout the investigated range. The payout times are
48
49 decreased ca. 50% in all cases from the lowest to the highest glycerol feedstock capacity, and the
50
51
52 annualized net profit per kg of product is increased by ca. 20%.
53
54
55
56
57
58
59
1
2
3 Profitability and environmental friendliness of the glycerol biorefinery. The profitability
4
5
6 and environmental impact of a biorefinery integrating all processes analyzed with a purified
7
8 glycerol capacity of 100 kt y−1 were evaluated by solving the optimization problem described in
9
10 eqs. 4−15, while gradually increasing the constraint on the GWP. The Pareto front between ANP
11
12
13
and GWP is presented in Figure 5. A significant trade-off between the two objectives is evident:
14
15 20% reduction of ANP and 7% increase in payout time result in 100% reduction of GWP. This
16
17 ‘GWP-neutral’ glycerol biorefinery is achieved when glycerol carbonate is co-produced with 1,2-
18
19
propanediol, the production line of the latter having a negative GWP (i.e., the negative values are
20
21
22 possible considering the environmental burden of the alternative scenario of glycerol waste
23
24 treatment). Similar trends were observed for CED and EI99, as presented in the SI, although zero
25
26 values of environmental impact were not reached in these metrics.
27
28
29 The respective product mix for the optimization scenarios is presented in Figure 6. It is
30
31 straightforward to note that glycerol carbonate dominates in all cases. When no constraint is
32
33 imposed to the GWP values (which led to a GWP of 1.20 kgCO2eq kgglycerol−1), a mono-product plant
34
35
36
is the most favorable solution, which coincides with the configuration inferred by Lari et al.,12 not
37
38 considering capital costs. When a more and more strict constraint on GWP is applied, allyl alcohol
39
40 and 1,2-propanediol appear in the optimal product mix along with glycerol carbonate. This is due
41
42
to the significantly greater potential for energy recovery between the processes targeting these two
43
44
45 chemicals compared to that possible within the sole glycerol carbonate production line. A product
46
47 mix favoring glycerol carbonate and 1,2-propanediol was also identified when focusing on
48
49 environmental impact and operating costs only.12 One reason for the similarity of previous and
50
51
52 current results at the glycerol refinery level is the fact that these two production lines have a
53
54 similarly low annualized capital cost per kg of product as a percentage of their profitability range
55
56
57
58
59
1
2
3 (i.e., 6 and 7% for 1,2-propanediol and glycerol carbonate, respectively). A neutral GWP impact
4
5
6 would be attained with a production mix comprising 65% glycerol carbonate and 35% 1,2-
7
8 propanediol based on this study, which corresponds to GWP ‘gain’ of ca. 5.8 kgCO2eq kgglycerol−1
9
10 compared to the traditional production of these two compounds. An equivalent environmental
11
12
13
benefit for the glycerol carbonate-1,2-propanediol mix has also been reported by Lari et al.12 The
14
15 uniformity of the findings is due to the fact that the GWP impact of the plant construction was not
16
17 considered in neither of the studies.
18
19
Besides for the compromise between economic and environmental metrics in the low GWP
20
21
22 scenarios, the annual production of the respective chemicals in the production mix is also worth
23
24 of mention. The amounts of 1,2-propanediol and allyl alcohol obtained in the more
25
26 environmentally-friendly biorefineries (7.8−27 and 1.2 kt y−1, respectively) are sufficiently high
27
28
29 to permit the introduction of these chemicals into local or global markets.
30
31 Capital cost estimation was conducted in this study for plants with crude glycerol capacities in
32
33 the range of 10−120 kt y−1. The lower boundary corresponds to the capacity of a biodiesel plant of
34
35
36
100 kt y−1 (i.e., considering the 1:10 glycerol:biodiesel mass ratio), which is a typical case based
37
38 on the size of the biodiesel plant from waste cooking oils in Hong Kong.32 In the US only, various
39
40 biodiesel plants produce 1−180 MMgy of biodiesel,36 the higher value corresponding to glycerol
41
42
productions of 50-60 kt y−1. Thus, in relation to production scale, the glycerol biorefinery
43
44
45 capacities examined in this study refer to amounts that can be supplied from one-two biodiesel
46
47 plants, depending on their geographical location and density. Concerning the production capacities
48
49 of the targeted chemicals (i.e., in the range 10−100 kt y−1 as seen also in Figure 6), they also match
50
51
52 their typical production scale. For instance, the construction of propanediol plants with a capacity
53
54 of 20 kt y−1 is currently considered.37
55
56
57
58
59
1
2
3 CONCLUSIONS
4
5
6 Aiming at the establishment of biorefineries transforming renewables into chemicals and fuels,
7
8 capital cost estimation is important already from early design stages. Together with operating costs
9
10 and environmental impact of the processes investigated, it can provide valuable information for
11
12
13
selecting superior production paths and product mixes. The lack of detailed data at early stages
14
15 makes this task cumbersome, considering also the uncertainty arising from the different capital
16
17 cost estimation approaches. This was clearly depicted in the present techno-economic study at
18
19
early design stages of a perspective glycerol biorefinery. The capital cost estimates for all the most
20
21
22 important chemical derivatives investigated deviate significantly depending on the estimation
23
24 method, the Taylor approach giving consistently higher values than the Guthrie and ACCE
25
26 methods. The deviation decreases as the plant capacity increases, but the Taylor protocol estimates
27
28
29 remain, in the best case, still 1.5-times higher than those attained with the other approaches.
30
31 According to the Guthrie method, all glycerol valorization routes analyzed are profitable. The
32
33 highest profit and environmental gain per kg of glycerol compared to the fossil based equivalent
34
35
36
production is achieved manufacturing glycerol carbonate. Heat integrated biorefinery layouts
37
38 provide incentives for co-producing 1,2-propanediol and allyl alcohol to further reduce the
39
40 environmental impact per kg of glycerol utilized by 100% with a compromise of only 20% on the
41
42
plant profitability. This initial screening of a perspective glycerol refinery can be used for detailed
43
44
45 techno-economic analysis at later design stages, including also additional economic factors such
46
47 as the optimal plant location with respect to glycerol transportation costs, as well as local and
48
49 global market conditions of the best targeted chemicals. In spite of the added value of these results,
50
51
52 the selection of optimal chemicals to be produced is substantially similar to what was indicated in
53
54 the previous assessment restricted to environmental metrics and operating cost. Since relevant
55
56
57
58
59
1
2
3 information can be obtained already with a more contained effort, life-cycle analysis should be
4
5
6 more widely applied to drive the development of emerging sustainable technologies.
7
8
9
10 ASSOCIATED CONTENT
11
12
13 Supporting Information. Modelling details for the individual processes, capital cost method
14
15 details, capital cost assessment of the individual production lines, and additional environmental
16
17
18 assessment metrics of the glycerol biorefinery (PDF).
19
20 AUTHOR INFORMATION
21
22
23 Corresponding Authors
24
25
26 *Cecilia Mondelli: cecilia.mondelli@chem.ethz.ch, Javier Pérez-Ramírez: jpr@chem.ethz.ch,
27
28 Stavros Papadokonstantakis: stavros.papadokonstantakis@chalmers.se.
29
30
31
32
33 ACKNOWLEDGMENT
34
35
36 S.C. D’Angelo thanks the IDEA League for the research exchange grant.
37
38
39
40 REFERENCES
41
42
43 1. REN21 Renewables 2017 Global Status Report; Paris, 2017; http://www.ren21.net/wp-
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47 16, 2018).
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15 Dihydroxyacetone over Technical Iron Zeolite Catalysts. React. Chem. Eng. 2016, 1 , 106-
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24 Acid Production from Glycerol Using Cascade Bio- and Chemocatalysis. Energy Environ.
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26 Sci. 2015, 8, 558-567, DOI 10.1039/c4ee03352c.
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29 22. Dreyer, L. C.; Niemann, A. L.; Hauschild, M. Z., Comparison of Three Different LCIA
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31 Methods: EDIP97, CML2001 and Eco-Indicator 99 - Does it Matter which One You Choose?
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38 Energy Demand in LCA: The Energy Harvested Approach. Int. J. Life Cycle Assess. 2015,
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40 20, 957-969, DOI 10.1007/s11367-015-0897-4.
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47 a Useful Indicator for the Environmental Performance of Products? Environ. Sci. Technol.
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6 of the Organic Chemical Industry. Energy 2003, 28, 721-740, DOI 10.1016/s0360-
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8 5442(02)00166-4.
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10 26. Pushkar, S., Using the Optional Steps of Eco-Indicator 99 to Evaluate the Operational Energy
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Consumption in Lifecycle Assessment Value Choices. J. Archit. Eng. 2015, 21, 05015002-
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15 1/-9, DOI 10.1061/(asce)ae.1943-5568.0000178.
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17 27. De Meester, S.; Callewaert, C.; De Mol, E.; Van Langenhove, H.; Dewulf, J., The Resource
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Footprint of Biobased Products: A Key Issue in the Sustainable Development of
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22 Biorefineries. Biofuels, Bioprod. Bioref. 2011, 5, 570-580, DOI 10.1002/bbb.304.
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24 28. Douglas, J. M., A Hierarchical Decision Procedure for Process Synthesis. AIChE J. 1985,
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26 31, 353-362, DOI 10.1002/aic.690310302.
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29 29. Douglas, J. M.; Stephanopoulos, G., Hierarchical Approaches in Conceptual Process Design:
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31 Framework and Computer Aided Implementation. AIChE Symp. Ser. 1995, 91,183-197.
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33 30. Biegler, L. T.; Grossmann, I.; Westerberg, A., Systematic Methods of Chemical Process
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Design. Prentice Hall PTR, 1997.
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38 31. Taylor, J. H., Process Step Scoring Method for Making Quick Capital Estimates. Eng.
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40 Process Econ. 1977, 2, 259-267, DOI 10.1016/0377-841x(77)90004-3.
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32. ASB Biodiesel Home Page. http://www.asb-biodiesel.com (accessed Sept 30, 2018).
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45 33. Zils, M. Moving toward a Circular Economy. McKinsey&Company.
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47 https://www.mckinsey.com/business-functions/sustainability-and-resource-
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49 productivity/our-insights/moving-toward-a-circular-economy (accessed Sept 30, 2018).
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3 34. Gu, K. C.; Vassiliadis, V. S., Limitations in Using Euler's Formula in the Design of Heat
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6 Exchanger Networks with Pinch Technology. Comput. Chem. Eng. 2014, 68, 123-127, DOI
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8 10.1016/j.compchemeng.2014.05.015.
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10 35. Gargalo, C. L.; Cheali, P.; Posada, J. A.; Gernaey, K. V.; Sin, G., Economic Risk Assessment
11
12
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of Early Stage Designs for Glycerol Valorization in Biorefinery Concepts. Ind. Eng. Chem.
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15 Res. 2016, 55, 6801-6814, DOI 10.1021/acs.iecr.5b04593.
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17 36. Biodiesel Magazine. U.S. Biodiesel Plants.
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http://www.biodieselmagazine.com/plants/listplants/USA (accessed Sept 30, 2018).
20
21
22 37. Reisch, M. S. Propanediol Plant Advances. C&EN Chemical and Engineering News.
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24 https://cen.acs.org/articles/96/i6/Propanediol-plant-advances.html (accessed Sept 30, 2018).
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1
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3 Table 1. Comparison of classification practices for capital cost estimates (adapted from ref. 15).
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5 AACE std. a ANSI std. Z94.0 ACostEb TRLc
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Class 5 OoMd OoMd TRL 1-4
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8 L: −20 to −50% −30/+50% Class IV Technology conception,
9 H: +30 to +100% −30/+30% laboratory validation
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11 Class 4 Budget Study TRL 5-6
12 L: −15 to −30% −15/+30% Class III Technology validation and
13 H: +20 to +50% −20/+20% demonstration
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15 Class 3 Budget TRL 7
16 L: −10 to −20% Class II Operational system
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18 H: +10 to +30% −10/+10% demonstration
19 Class 2 Definitive Definitive TRL 8
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21 L: −5 to −15% −5/+15% Class I System completion and
22 H: +5 to +20% −5/+5% qualification
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24 Class 1 TRL 9
25 L: −3 to −10% Actual system operation
26 H: +3 to +15%
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aL = low, H = high. bACostE = Association of Cost Engineers (UK). cTRL = technology readiness
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29 level. dOoM = order of magnitude.
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3 Table 2. Operating cost and environmental life-cycle impact metrics for the single production lines
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5 with heat integration. The values in parenthesis refer to fossil based production (except from the
6 case of the lactic acid processes P1 and P2, for which the metrics refer to the industrially applied
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8
manufacture based on sugar beet).
9 Process Operating cost CED GWP EI99
10 ($ kgproduct−1) (MJeq kgproduct−1) (kgCO2eq kgproduct−1) (points kgproduct−1)
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12 P1 0.39 −2.2 (109) −0.2 (7.6) −0.17 (0.53)
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P2 -0.23 123.0 (109) 6.2 (7.6) 1.05 (0.53)
15 P3 0.89 26.0 (64) 2.2 (2.3) −0.04 (0.23)
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P4 -9.32 −73.1 (84) 1.3 (2.8) −0.93 (0.29)
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18 P5 0.31 −38.7 (100) −2.8 (4.1) −0.17 (0.33)
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20
P6 2.66 183.1 (88) 10.8 (3.2) 1.22 (0.26)
21 P7 0.75 20.2 (128) 1.1 (5.7) −0.11 (0.26)
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3 Table 3. Purified glycerol requirements and economic metrics for the single production lines with
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5 heat integration. The annualized capital cost refers to a glycerol plant of 100 kt y−1. The purified-
6 to-crude glycerol ratio is 0.81.
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8 Process Glycerol to Annualized Price of Profit per Profit per
9 product ratio capital cost product product glycerol
10 (kg kg−1) ($ kgproduct−1) ($ kgproduct−1) ($ kgproduct−1) ($ kgglycerol−1)
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12 P1 1.56 0.05 1.8 1.35 0.87
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P2 2.40 0.52 1.8 1.51 0.63
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15 P3 2.00 0.10 1.5 0.51 0.26
16 P4 8.69 3.3
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1.56 11.06 1.27
18 P5 1.28 0.06 1.4 1.03 0.81
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P6 1.97 0.72 4.5 1.11 0.57
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21 P7 0.79 0.12 2.4 1.53 1.94
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Figure 1. Chemocatalytic production lines integrated in the glycerol biorefinery assessed in this
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28 work.
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24 Figure 2. Capital cost investment for a) 1,2-propanediol and b) glycerol carbonate production
25 according to the three costing methods applied in this study for various crude glycerol feedstock
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capacities (the purified-to-crude glycerol ratio is 0.81).
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24 Figure 3. Capital cost decomposition of the single production lines into three equipment categories
25 (reactors, separation columns, and auxiliary equipment units) for the glycerol feedstock capacities
26 investigated. The values correspond to the 10−100 kt y−1 range of purified glycerol feedstock, the
27 purified-to-crude glycerol ratio being 0.81. The lines are in aggregated form, i.e., the line for the
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reactors only refers to reactor equipment, the line for the separation columns refers to both reactor
30 equipment and separation columns and the line for the auxiliary equipment refers to the total cost
31 of equipment.
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24 Figure 4. Profitability assessment of the single production lines for the glycerol feedstock
25 capacities investigated. The values correspond to the range 10-100 kt y−1 purified glycerol
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27 feedstock, the purified-to-crude glycerol ratio being 0.81.
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17 Figure 5. Pareto front between the annual net profit and the GWP of a glycerol biorefinery with a
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19 feedstock capacity of 100 kt y−1.
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19 Figure 6. Product mix of the glycerol biorefinery with a feedstock capacity of 100 kt y−1 under
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various constraints with respect to GWP. The numbers in the bars denote the annual productions
22 of the target chemicals in kt.
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1
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3 FOR TABLE OF CONTENTS USE ONLY
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23 Targeting glycerol carbonate, 1,2-propanediol, and allyl alcohol maximizes the profit and
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minimizes the ecologic impact of a prospective biorefinery valorizing glycerol to chemicals.
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