Heuristics to Guide the Development of Sustainable, Biomass-Derived

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Heuristics to Guide the Development of Sustainable, Biomass-Derived Platform Chemical Derivatives Sampath Gunukula, Hemant P. Pendse, William J DeSisto, and M. Clayton Wheeler ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.8b00412 • Publication Date (Web): 27 Feb 2018 Downloaded from http://pubs.acs.org on February 28, 2018

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ACS Sustainable Chemistry & Engineering

Heuristics to Guide the Development of Sustainable, Biomass-Derived Platform Chemical Derivatives Sampath Gunukulaa,b, Hemant P. Pendsea,b, William J. DeSistoa,b, M. Clayton Wheelera,b* a Department of Chemical and Biomedical Engineering, University of Maine, 5737 Jenness Hall, Orono, ME 04469 USA b Forest Bioproducts Research Institute, University of Maine, 5737 Jenness Hall, Orono, ME 04469 USA *Corresponding Author [email protected] Abstract Hundreds of catalytic routes to upgrade biomass derived platform chemicals have been proposed. In this study, we developed process selection and development heuristics for these catalytic transformations from techno-economic analysis of catalytically upgrading furfural (a potential platform chemical) to eight derivatives that vary in chemical functionality and process complexity. These heuristics included simple cost equations based on catalyst performance as well as process complexity to predict the minimum selling price of platform chemical derivatives. Additionally, design rules were developed to guide the development of catalytic technologies for upgrading platform chemicals. The conversion of platform chemicals to hydrocarbons must be avoided. For commercial relevance, attaining catalyst yield of 60% and weight hourly space velocity of at least on the order of 0.1 h-1 are necessary. Precious metal catalysts, such as Pt, cannot be used if the desired platform chemical derivative is priced below 1.00 (US$/kg). Finally, it has been learned that the feasible plant size of platform chemical production is comparable to that of a lignocellulosic based biofuel production.

KEYWORDS: Bio-based building blocks, Furfural, Levulinic acid, Succinic acid, 2methyltetrahydrofuran (MTHF), tetrahydrofurfuryl alcohol

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INTRODUCTION The non-renewable petroleum feedstocks such as coal and crude oil are converted to 8 to 9 foundation chemicals from which almost all industrial chemicals can be derived.1 The price volatility of petroleum feedstocks and growing concerns over climate change impacts with the use of petroleum feedstocks have led to the development of sustainable technologies to produce sugar derived chemicals that have potential to replace petroleum derived chemicals.1 Like the concept of foundation chemicals in the petrochemical industry, the idea of biobased building block or platform chemical from which a suite of industrial chemicals can be made was introduced to accelerate the growth of the bio-economy.1 Werpy et al. have originally identified a list of twelve platform molecules that can be produced from biomass derived sugars either using biological or chemical conversion pathways. Recently, Bozell and Petersen have revised this original list of potential biobased platform molecules.2 Hundreds of chemical catalytic pathways have been proposed to make chemicals and fuels from the identified potential platform molecules.1,2 A large amount of money and time is required to develop and commercialize a catalytic pathway for the conversion of a platform chemical to high-value-added products.3 Thus, it is important to assess economic potential of the proposed catalytic route as early as possible to avoid potential waste of research and development investments. Moreover, setting performance targets in terms of desired yields and catalyst rates to the research teams is necessary to reduce resources in time and money needed for the development of a new catalytic upgrading pathway of a platform molecule.4 It requires skills of process modeling and techno-economic analysis for assessing the economic potential of new catalytic upgrading pathways as well as for setting performance targets.4 However, technology development teams in general do not possess such skills. Additionally, it is

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impractical to evaluate hundreds of proposed catalytic routes for upgrading platform molecules. Thus, there is a need for both determining general performance targets and developing simple cost equations that can be used by research and development teams to determine the economic potential of a new catalytic route for converting platform molecule to a desired product. A few techno-economic studies have been published to determine the economic viability of producing platform molecules and of transforming these molecules to chemicals and fuels.5,6 None of these reports, however, have attempted to determine feasible plant scale and corresponding production cost at which platform molecules must be produced such that these molecules can be used as a feedstock in the sustainable production of chemicals and fuels. In general, economies of scale can be achieved with a large scale chemical production.7 However, diseconomies of scale associated with transportation distances might reduce achieving economies of scale in the production of platform molecules.7,8 Thus, the feasible size of a platform chemical plant, and corresponding production cost, is largely reliant on the transportation distance, which in turn will depend on the bulk density of a feedstock, crop yield, and the fraction of land used to produce the feedstock.8 In the current study, we perform techno-economic analysis of synthesis of a potential platform molecule furfural (FUR) and eight FUR derivatives in hope of finding simple cost equations and general rules of thumb in terms of catalyst yields and rates. These cost equations and generalities can be used to guide the development of catalytic pathways for upgrading platform molecules to value added chemicals and fuels.



DEVELOPMENT OF PROCESS AND COST MODELS Production of furfural A wide range of processes are proposed to make FUR from biomass.9,10 However, the possibility of achieving higher yields made biofine process more attractive than other processes. Biofine LLC. has demonstrated Acid Hydrolysis and DeHydration (AHDH) at the pilot scale to produce FUR, levulinic acid (LA), and formic acid (FA) from C5 and C6 sugars of lignocellulosic feedstocks using dilute sulfuric acid at a high temperature and pressure.11-14 A process flow diagram (PFD) was developed to produce FUR, LA, and FA from wood using AHDH technology following published literature (Figure S1).11-16 The detailed description of PFD is included in the supporting information. Production of furfural derivatives The aldehyde group and aromatic ring functionalities of FUR allow this platform molecule to be transformed into a great number of fuels and chemicals. A suite of more than 80 value-added chemicals and fuels that can be directly and indirectly derived from FUR have been identified.10 It is a daunting task to evaluate the economic potential of these FUR transformations. We, therefore, qualitatively screened possible FUR derivatives based on the criteria of: 1) Chemicals and fuels that have near term commercial potential and can be made from FUR either in one, two, or three steps of transformations, and 2) FUR derivatives that are either currently made from petroleum-based feedstocks or molecules that currently do not have a big market but have a potential to become a commodity molecule in near future. Following these criteria, we selected eight FUR derivatives listed in Table 1 that are representative of a wide range of such derivatives. Simplified PFDs were created to produce each selected furfural derivative, using published information (Figures S2, S3, S4, S5, S6, S7, S8, and S9).


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Descriptions of the PFDs are also included in the supporting information. Table 1 summarizes the important process information regarding the production of FUR derivatives Process simulation and cost estimation ASPEN Plus was used to simulate the processes of production of FUR and the production of FUR derivatives.27 In this analysis, the capacity of 1000 metric ton per day of bone dry wood for FUR production plant and the capacity of 240 metric ton per day of FUR for FUR derivatives production plant were assumed. The NRTL method was employed to model thermodynamics of analyzed production processes. The material and energy balances of catalytic reactors were determined using RSTOIC reactor model in ASPEN Plus as the kinetic data for most analyzed catalytic conversions were not available in the literature. The total amount of catalyst for each analyzed production process was calculated from weight hourly space velocity (WHSV) of catalysts. The simulated material balances as well as WHSVs of catalysts were used to size the catalytic reactors. The in-built cost estimator in ASPEN Plus was used to determine the installed cost of process equipment except catalytic reactors. The costs of catalytic reactors and catalysts used in the production processes were calculated using information obtained from several resources.28-29 Factors based on installed equipment cost were employed to determine the total capital investment of production processes (Table S2). In this study, all costs are reported in U.S. 2016 dollars. this The utility costs were determined using the simulated energy balances. The assumptions for calculating the operating costs of all analyzed production processes and the annualized costs of FUR can be found in the supporting information (Table S3 and Table S4). The 10-year average prices of raw materials and utilities were used to determine the operating costs (please refer supporting information for the justification of the use of average values). The 5 ACS Paragon Plus Environment


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discounted cash flow analysis method with an internal rate of return of 10% was employed to estimate the minimum selling price (MSP) of potential FUR derivatives. The MSP of potential FUR derivatives were compared against the average market prices of FUR derivatives to determine the economic viability of a process for the conversion of FUR. Please refer supporting information for the explanation justifying such comparison. Modeling of plant and transportation costs at different scales Economies of scale mean that operating and capital costs increase at a lower rate as the plant size increases, and the effect is usually estimated according to Equation 1. The biomass feedstock does not come to the chemical production facility from a single field located at a fixed distance from the production facility. Instead, biomass will be procured from a large area surrounding the chemical production facility. The total area in the environs of the production facility for procuring feedstock is dependent on the average crop yield and the proportion of land used to produce feedstock.6 Thus, transportation cost per unit of feedstock increases as the size of the plant increases because the feedstock must be transported from increasingly greater distances (Equation 2). The power law exponent (m) might be 2 if the feedstock is sparsely distributed around the chemical production facility.30 The value of m can be reduced to close to zero with a plantation approach where the chemical production facility controls a large feedstock production area and small scale plants.6 ℎ = × Transportation cost at the required size = Transportation cost at original size ×

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RESULTS AND DISCUSSION Material and energy balances and cost estimation of FUR production


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Conversion of 1000 metric tons (MT) of bone dry wood via AHDH results in the production of 125 MT of FUR, 245 MT of LA, and 97 MT of FA. The simulations are shown that separation yields of 95% by weight of FUR, 97% by weight of LA, and 72% by weight of FA can be achieved with the chosen separation and purification scheme. The purity of greater than 98% for FUR and LA and of 90% for FA can be achieved. It is assumed that FA with 90% purity can be sold at a market price of $0.60 kg-1.31 The pinch analysis indicates that 1×109 kJ/hr of process heat must be supplied from utilities. The char produced, with an assumed higher heating value (HHV) of 24 MJ/kg, is burned to generate a high-pressure steam.11 The process heat demand is satisfied by 65% of the generated high-pressure steam. The remaining steam drives an electric turbine. The boiler and turbine efficiencies were assumed to be 80% and 85%, respectively.

32

A total of 35 MW of electricity is generated, of which 8 MW is needed to meet

the electricity requirement of the process. The remaining electricity is assumed to be sold to a grid at a fixed price of $0.06 kWh-1. The estimated capital cost of FUR and LA production plant is $232 million (MM) (Table S1 and Table S2). The mass-based allocation approach is used to calculate the annualized costs of FUR and LA.33-34 The annualized costs of FUR and LA are assessed at $0.76 kg-1. This value is assumed as the FUR feedstock cost while estimating the MSP of FUR derivatives. Cost estimation of FUR derivatives The fixed capital investment and catalyst costs are summarized in Table S5. Please refer to supporting information for more information about capital and catalyst costs. The fixed capital investment of processes to produce analyzed FUR derivatives ranges from $17 MM to $118 MM. The assessed fixed capital investment to produce furfuryl alcohol is low, as compared to other analyzed FUR derivatives. The capital cost to produce furfuryl alcohol is relatively low



because the conversion and selectivity are high, so separations are simple (Please refer supporting information for more information about separations). In addition, the reactor costs are low as only one FUR conversion step is needed to produce furfuryl alcohol and a concentrated FUR feed can be used. The capital costs to produce maleic anhydride is nearly twice as high as that of furfuryl alcohol production though one FUR conversion step is needed. The low selectivity to maleic anhydride as compared to furfuryl alcohol selectivity and the requirement of pressure swing adsorption to generate pure oxygen for the oxidation of FUR increase the capital cost requirement to produce maleic anhydride. Guidelines to research and development teams The comparison of MSP of FUR derivatives against the respective market prices indicates that the production of LA and alkanes from FUR may not be potential opportunities, as the estimated MSPs of these FUR derivatives are higher than the current average target market prices (Figure 1). The assessed MSP of LA produced from FUR is higher than the target price even though high LA yields and high reaction rates are attained (Table 1 and Figure 1). When the number of FUR conversion steps to make alkanes is reduced from 3 to 1, the MSP of alkanes is decreased from $1.58 to $1.29 kg-1, which is still higher than the target price of alkanes. Thus, investments to develop FUR transformation pathways to produce platform chemicals and super commodity chemicals must be avoided. An overall catalyst selectivity of at least 60% is necessary to achieve economic viability of processes to produce FUR derivatives. It is found that the variable costs contribute at least 83% to the MSP of analyzed FUR derivatives (Figure 1). Breaking down variable costs into individual cost components indicates that the contribution of feedstock (FUR) cost is at least 70% of the total variable costs for all analyzed processes to produce FUR derivatives. Thus, FUR 8 ACS Paragon Plus Environment

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selectivity to a desired chemical and the FUR price can highly influence the economics of the processes to produce FUR derivatives. Further analysis shows that when catalyst selectivities to FUR derivatives falls below 60%, the MSP of all analyzed FUR derivatives except THF production are found to be greater than the target market prices of respective FUR derivatives (Table S6). Thus, research and development teams must attain catalyst selectivities of at least 60% to attain economic viability of FUR derivatives with a market price between $1.00 kg-1 and $ 2.00 kg-1. The use of precious noble metal catalysts should be avoided, when the FUR derivative is a low-value added chemical with a market price of less than $1.00 kg-1. Additionally, such chemicals must be made only in one FUR conversion step. The estimated MSP of furfuryl alcohol made from FUR is $0.98 kg-1, which is less than the market price of furfuryl alcohol (Figure 1). Combined, high FUR conversion, high selectivity to furfuryl alcohol, one FUR conversion step, and the use of inexpensive catalyst (Cu/MgO) all result in low capital and operating costs of furfuryl alcohol production, as compared to other analyzed FUR derivatives. If the Cu/MgO catalyst is replaced with an expensive Pt catalyst and assuming that the WHSV of the Pt catalyst is same as that of Cu/MgO, the MSP of furfuryl alcohol is increased to $1.16 kg-1. This result demonstrates that even at a high WHSV, it is likely not economically viable to make furfuryl alcohol using precious metal catalysts. Research and development teams can select expensive metal catalysts for the conversion of FUR to high value-added chemicals with a market price above $1.25 kg-1. When one noble metal is used for FUR conversion as in the case of MA and LA production, the estimated MSP of FUR derivatives is found to be around $1.25 kg-1. The MSP of FUR derivatives is estimated to be around $1.6 kg-1 when two noble metal catalysts are needed for the conversion of FUR to 9 ACS Paragon Plus Environment


alkane, diol, and 2-MTHF (Figure 1). Though it seems possible to use multiple noble metal catalysts to produce high-value added FUR derivatives, the capital risk and the barriers to entry can be high when more than one precious metal catalyst is employed for FUR conversion due to increase in the fixed capital investment. The catalyst technology development teams must achieve high FUR conversions (≈100%) and high WHSV for precious metal catalysts to be commercially feasible. However, conversion and WHSV are less important when the product that has a market price of $4.00 kg-1 such as THF. Recovery of unconverted FUR is necessary when its conversion is below 100%, as the overall yield (conversion×selectivity) majorly impacts the production cost of FUR derivatives. The addition of a FUR recovery step significantly increases production cost, unless it is easy to separate unconverted FUR as in the case of alkanes production (Please refer supporting information for more information). The difference between the estimated MSP and the target market price of most analyzed chemicals is very small that the addition of another separation step may not be economically viable. When the WHSV for precious metal catalyst falls below the value on the order of 10-1 g/(g- catalyst⋅h) or 100 g/(g-active metal⋅h), it is found that the catalyst cost is increased by a factor of 10. Such a rise in the catalyst cost will increase the estimated MSP of FUR derivatives to greater than $2.3 kg-1. The comparison of MSP of FUR derivatives against market prices indicates that except THF no other FUR derivative is economically viable for the MSP of greater than $2.3 kg-1. Thus, research and development teams must achieve high reaction rates when FUR is converted over a precious metal catalyst. The use of general guidelines The general guidelines are summarized as follows: 1. Catalyst selectivity to a target product of platform chemical conversion must be greater than 60% for commercial relevance 10 ACS Paragon Plus Environment

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2. The nearly complete catalytic conversion of a platform chemical is necessary 3. Catalyst WHSV on the order of 0.1 g g-1 h-1 must be attained for commercial relevance since an exponential increase in the cost is found when the catalyst rates fall below about 0.1 g g-1 h-1 4. It is not economically viable to target super commodity chemicals and other platform chemicals 5. An inexpensive catalyst must be used for the platform chemical upgrading if the targeted platform chemical derivative is less than $1.00 kg-1 6. Expensive noble metal catalysts can be employed for the conversion of a platform chemical to an end chemical with a market price above $1.25 kg-1 These guidelines can be used for the selection of potential targets for the development of platform chemical conversion pathways, when the cost of making a platform chemical is close to that of FUR. In addition, these generalities can be used to set performance targets for the development of transformation pathways of platform chemicals. For example, LA is a platform molecule and it can be made to a wide range of chemicals including succinic acid and 2MTHF.36,37 It is economically unviable to pursue the development of a pathway to convert LA to succinic acid, as succinic acid is a platform chemical like FUR and LA.1 The market price of 2MTHF is $1.8 kg-1.35 Thus, research and development teams can use up to two precious metal catalysts for the conversion of LA to 2-MTHF. In addition, these teams must achieve close to 100% conversion of LA, greater than 60% selectivity to 2-MTHF, and WHSV on the order of 101

g/(g- catalyst⋅h) or 100 g/(g-active metal⋅h), to make production of 2-MTHF form LA

commercially feasible. General cost equations The MSP of a potential platform chemical derivative can be divided into variable and fixed costs. The fixed costs include cost of capital, depreciation costs, and other fixed operating costs such as labor charges.28 The cost of capital can be calculated separately for fixed capital investment that accounts costs of equipment, installation, buildings, etc., and the costs of precious catalysts. The costs of feedstock (platform chemical), co-reactants such as hydrogen, 11 ACS Paragon Plus Environment


utilities, wastewater treatment, catalyst support, and an inexpensive catalyst such as copper chromite and nickel constitute the total variable cost of a potential platform chemical derivative production. Cost equations, generalized using the information obtained from the FUR derivatives analyzed in this work, are presented in Table 2 and can be used to make preliminary MSP estimates for other potential platform chemical derivatives. The cost contributions of feedstock and other co-reactants to the MSP of a platform chemical derivative are expressed in terms of prices and yields. For the yields, the feedstock conversion should be close to 100%, or it should be simple to recycle unconverted feedstock as in the case of production of alkanes (Please refer supporting information for more information). For feedstock conversion below about 95%, we recommend estimating the additional capital and operating costs to recycle the unconverted feed and then estimate the annualized cost of capital. Finally, add these annualized costs of capital and additional operating costs to the MSP of a platform chemical derivative estimated using the cost equations listed in Table 2. The cost contribution of the use of precious metal catalysts (Pt, Pd, Rh, Ru, Re) to the MSP of a platform chemical can be determined by using equations listed in Table 2. The incremental fixed costs of a process to produce a FUR derivative are calculated for WHSV values ranging from 0.1 to 1.5 g (g- catalyst⋅h)-1. The economic analysis of FUR derivatives is shown that there is a negligible impact on the fixed cost of a potential FUR derivative, when the value of WHSV of expensive metal catalysts is increased beyond 1.5 g (g- catalyst⋅h)-1. Thus, incremental fixed costs are estimated for WHSV values up to 1.5 g (g- catalyst⋅h)-1. The 10-year average prices of precious metal catalysts are employed for estimating the incremental fixed costs.38 It is assumed that there is no catalyst deactivation and the salvage value of catalyst at the 12 ACS Paragon Plus Environment

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end of the plant life of 20 years is subtracted from the initial catalyst cost. A power function is fitted to the data of WHSV and incremental fixed costs to obtain equations for catalyst cost contribution to the MSP of a platform chemical derivative (Table 2). The costs of utilities, wastewater treatment, reactor, separations, inexpensive catalysts, and catalyst support as well as fixed costs other than the cost of capital for the total investment of precious catalysts to produce analyzed furfural derivatives are grouped into the additional cost (Ac). The additional cost is then plotted against the total number of required process steps to produce a FUR derivative. Such process steps are determined by counting number of process steps involved in the production of a target chemical. Each process step consists of a catalytic reactor followed by subsequent separation and purification step. For example, furfuryl alcohol production has only one process step as FUR is directly hydrogenated to furfuryl alcohol in a catalytic reactor followed by a condenser to separate furfural alcohol from unreacted hydrogen.18 Whereas, the LA production has two process steps: conversion of FUR to ethyl levulinate and the production of LA acid from ethyl levulinate.10,19 When fitting the data for the cases studied here, a straight line based on the number of process steps is sufficient to represent the additional costs (Table 2). The cost contributions of feedstock, co-reactants, and catalyst are added to the additional cost component to obtain MSP of a potential platform chemical derivative (Table 2). The MSPs of FUR derivatives are predicted using cost equations presented in Table 2. The predicted MSPs are found to be within ± 5% of the MSPs of FUR derivates that are estimated from the detailed techno-economic analysis (Figure 2). Thus, the cost equations listed in Table 2 can be used to determine the economic potential of transformation pathways of platform chemicals at the early stages of process development. The data (stoichiometry, number



of process steps, selectivity, type of catalysts, and WHSV) available at the laboratory stage of process development are sufficient for the application of cost equations listed in the Table 2. The application of cost equations presented in Table 2 for the prediction of MSP of a platform chemical derivative is described through an arbitrary example. Consider the conversion of a platform chemical over Pt (5wt.%)/C catalyst to a platform chemical derivative via hydrogenation. It is assumed that the conversion, selectivity, hydrogen consumption, and WHSV of this arbitrary route at the laboratory stage of technology development are 100%, 90%, 0.2 g per gram of a platform chemical derivative, and 0.8 h-1, respectively. Additionally, the price of a platform chemical and the price of hydrogen are assumed at $1 kg-1 and $2.5 kg-1, respectively. The predicted MSP of the platform chemical derivative using cost equations is found to be $1.8 kg-1 for these process and economic parameter values. Please refer supporting information for the detailed calculations to obtain the MSP of the assumed arbitrary platform chemical derivative. The cost equations can be applied to predict the economic viability of a new process for the conversion of a platform chemical using a chemical catalyst at the technology readiness levels (TRL) of 2 and 3. We recommend the use of a detailed techno-economic analysis with rigorous calculations of thermodynamics and accurate estimations of capital and operating costs to make a decision on the transition of a new process for the conversion of a platform chemical using a chemical catalyst from the development stage of TRL 4 to TRL 5. Please refer supporting information for the definition of TRL stages. Impact of plant scale The impact of plant scale on the annualized cost of FUR is determined by estimating the annualized cost of FUR for a range of wood conversion plant capacities (Figure S10). The sixtenths rule (value of n in equation 1 is equal to 0.6) is employed to determine capital cost for 14 ACS Paragon Plus Environment

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making FUR at different plant scales by considering capital investment for 1000 metric ton per day of wood conversion plant as a base case.30 In equation 2, m = 1 for plant scales larger than 100 metric ton per day of wood conversion by assuming a significant fraction of wood grown in the land surrounded by the plant is dedicated to the production of FUR.30 For plants with a scale smaller than 100 metric ton per day, m = 0. The annualized cost of FUR produced in a plant with a capacity of 2000 metric ton per day of wood conversion is estimated at $0.60 kg-1. The production of commodity chemicals like alkanes and platform chemicals like LA from FUR is not economically viable even FUR is produced at a scale of 2000 metric ton per day of wood conversion (Table S7). The plant scale of 1000 metric ton of wood conversion to produce FUR at the annualized cost of $0.76 $ kg-1 is found to be sufficient for the feasible production of all analyzed FUR derivatives except alkanes and LA (Table S6). This finding indicates that plant scales comparable to that of biofuels can be needed to produce platform chemicals to be economically attractive. Supporting Information The catalyst cost accounting, figures and description of process flow diagrams, the justification of the use of average values for economic variables, definition of technology readiness level, separation costs of production of furfural derivatives, comparison of minimum selling price of furfural derivatives with the average market prices, sensitivity analysis, and an example of application of simple cost equations. Acknowledgements The authors acknowledge kaveh dalvand and Jonathan Rubin for their support on obtaining market information for the furfural derivatives. This work was also supported by funding from the National Science Foundation, Sustainable Energy Pathways (1230908).



References (1) Top Value Added Chemicals from Biomass. Vol. I-Results of Screening for Potential Candidates from Sugars and Synthesis Gas. NREL/TP-510-35523; National Renewable Energy Lab: Golden, CO, 2004; http://www.nrel.gov/docs/fy04osti/35523.pdf (accessed 05/ 30/2017). (2) Bozell, J.; Petersen, G. Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited. Green Chem. 2010, 12, DOI10.1039/B922014C. (3) From the sugar platform to biofuels and biochemicals: Final report for the European commission. Contract no. ENER/C2/423-2012/S12.673791, 2015; https://ec.europa.eu/energy/sites/ener/files/documents/EC%20Sugar%20Platform%20final%20re port.pdf (accessed 02/19/2018) (4) Gunukula, S.; Anex, R. Evaluaitng and guiding the development of sustainble biorenewable chemicals with feasible space analysis. Biochem. Eng. J. 2017, 119, DOI 10.1016/j.bej.2016.12.012. (5) Tribl, C.; Nikolakis, V.; Ierapetritou, M. Simulation and economic analysis of 5hydroxymethylfurfural conversion to 2,5-furandicarboxylic acid. Comput. Chem. Eng. 2013, 52, DOI 10.1016/j.compchemeng.2012.12.005. (6) Efe, C.; van der Wielen, L.A.M.; Straathof, A.J.J. Techno-economic analysis of succinic acid production using adsorption from fermentation medium. Biomass Bioenergy 2013, 56, DOI 10.1016/j.biombioe.2013.06.002. (7) Jenkins, B.M. A Comment on the optimal sizing of a biomass utilization facility under constant and variable cost scaling. Biomass Bioenergy 1997, 13 (1-2), DOI 10.1016/S09619534(97)00085-8. (8) Richards, T. Challenges in scaling up biofuels infrastructure. Sci. 2010, 329 (5993), DOI 10.1126/science.1189139. (9) Yan, K.; Jarvis, C.; Gu, J.; Yan, Y. Production and catalytic transformation of levulinic acid: A platform for specialty chemicals and fuels. Renew. Sustain. Energy Rev. 2015, 51, DOI 10.1016/j.rser.2015.07.021. (10) Mariscal, R.; Maireles-Torres, P.; Ojeda, M.; Sadaba, I.; Granados, M. L. Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels. Energy Environ. Sci. 2016, 9, DOI 10.1039/C5EE02666K (11) Hayes, D.; et al.. The Biofine Process – Production of levulinic acid, furfural, and formic acid from lignocellulosic feedstocks biorefineries. In Biorefineries-Industrial Processes and


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Products: Status Quo and Future Directions; Kamm, B., Gruber P. R. R., Kamm M., Eds.; Wiley-VCH Verlag GmbH:Weinheim, Germany, 2005 (12)

Fitzpatrick, S. US Patent 5608105, 1997.

(13)

Fitzpatrick, S. US Patent 4897497, 1990.

(14) Girisuta, B.; Janssen, L.; Heeres, H. Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid. Ind. Eng.Chem. Res. 2007, 46 (6), DOI 10.1021/ie061186z (15) Laitinen, A.; Penttilä, K.; Kaunisto, J. Physical solvent extraction of levulinic acid from dilute aqueous solution with 2-methyltetrahydrofuran. Separation Sci. Technol. 2016, 51 (3), DOI 10.1080/01496395.2015.1105264. (16) Hladiy, S.; Starchevskyy, M.; Pazderskyy, Y.; Lastovyak, Y. US Patent 6713649 B1, 2004. (17) Nagaraja, B. M.; Siva Kumar, V.; Shashikala, V.; Padmasri, A. H.; Sreedhar, B.; David Raju B.; Rama Rao, K. S. A highly efficient Cu/MgO catalyst for vapor phase hydrogenation of furfural to furfuryl alcohol, Catal. Commun. 2003, 4 (6), DOI 10.1016/S1566-7367(03)00060-8. (18) Chen, B.; Li, F.; Huang, Z.; Lu, T.; Yuan Y.; Yuan, G. Integrated Catalytic Process to Directly Convert Furfural to Levulinate Ester with High Selectivity. ChemSusChem, 2014, 7, DOI: 10.1002/cssc.201300542. (19) Alonso-Fag ndez, N.; Granados, M. L.; Mariscal R.; Ojeda, M. Selective conversion of furfural to maleic anhydride and furan with VOx/Al2O3 catalysts. ChemSusChem, 2012, 5 (10), DOI 10.1002/cssc.201200167 (20)

Ozer, R. US Patent 8710251 B2, 2014.

(21)

Fischer, R.; Pinkos, R. US Patent 5905159 A,1999.

(22)

Dunlop, A.P.; Huffman, G.W. US Patent 3257417 A, 1996.

(23) Wabnitz, T.; Breuninger, D.; Heimann, J.; Backes, R.; Pinkos, R. US Patent 8168807 B2, 2012. (24) Chen, X.; Sun, W.; Xiao, N.; Yan, Y.; Liu, S. Experimental study for liquid phase selective hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol on supported Ni catalysts. Chem. Eng. J. 2007, 126 (1), DOI 10.1016/j.cej.2006.08.019. (25) Liu, S.; Amada, Y.; Tamura, M.; Nakagawa, Y.; Tomishige, K. Performance and characterization of rheniummodified Rh–Ir alloy catalyst for one-pot conversion of furfural into 1,5-pentanediol. Catal. Sci. Technol. 2014,4, DOI 10.1039/C4CY00161C. (26) Huber, G.W.; Chheda, J.N.; Barrett, C.J.; Dumesic, J.A. Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates. Sci. 2005, 308 (5727), DOI 10.1126/science.1111166.



(27)

Aspen Plus® v.9, AspenTech Inc.

(28) Turton, R.; Bailie, R.; Whiting, W.; Shaeiwitz, J.; Bhattacharyya, D. Analysis Synthesis and Design of Chemical Processes, 4th ed.;, Upper Saddle River, New Jersey, 2012. (29) Process design and economics for the conversion of lignocellulosic biomass to hydrocarbon fuels, PNNL-23053, 2013; https://www.nrel.gov/docs/fy14osti/61178.pdf (accessed 2/19/2018) (30) Wright, M.; Brown, R.C. Establishing the optimal sizes of different kinds of biorefineries. Biofuels Bioprod. Biorefining 2007, 1 (3), DOI 10.1002/bbb.25. (31)

ICIS chemical business. https://www.icis.com/subscriber/icb, 2017 (accessed06/24/2017)

(32) Process design and economics for biochemical conversion of lignocellulosic biomass to ethanol- Dilute acid pretreatment and enzymatic hydrolysis of corn stover. NREL/TP-510047764; National Renewable Energy Lab: Golden, CO, 2011; https://www.nrel.gov/docs/fy11osti/47764.pdf (accessed 02/19/2018) (33) Yang, M.; You, F. Comparative techno-economic and environmental analysis of ethylene and propylene manufacturing from wet shale gas and naphtha. Ind. Eng. Chem. Res. 2017,56, DOI 10.1021/acs.iecr.7b00354. (34) Gunukula, S.; Runge, T.; Anex, R. Assessment of biocatalytic production parameters to determine economic and environmental viability. ACS Sustainable Chem. Eng. 2017, 5, DOI 10.1021/acssuschemeng.7b01729 (35) Identification and market analysis of most promising added-value products to be coproduced with the fuels. Bioref-Integ, 2017; http://www.bioref-integ.eu/fileadmin/biorefinteg/user/documents/D2total__including_D2.1__D2.2__D2.3_.pdf (accessed 6.24.17) (36) Dutta, S.; Wu, L.; Mascal, M. Efficient, metal-free production of succinic acid by oxidation of biomass-derived levulinic acid with hydrogen peroxide. Green Chem. 2015,17, DOI 10.1039/C5GC00098J (37) Phanopoulos, A.; White, A. J. P.; Long, N. J.; Miller, P. W. Catalytic Transformation of Levulinic Acid to 2-Methyltetrahydrofuran Using Ruthenium–N-Triphos Complexes. ACS Catal. 2015, 5, DOI 10.1021/cs502025t. (38) Johnson Matthey. http://www.platinum.matthey.com/prices/price-charts, 2017 (accessed 6.26.2017)


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Page 19 of 23 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Tables Table 1. Important process information for production of FUR derivatives Chemical

Overall conversion

Overall selectivity

Furfuryl alcohol Levulinic acid

0.99

1

No. of process steps 1

Reactor 1 WHSVa

Reactor 2 WHSV

Reactor 3 WHSV

1

0.89

2

2-MTHF

1

0.72

2

THF

1

0.61

2

THFA

0.99

1

MA

1

Diol

1

Source

4.8 [Cu/MgO]

-

-

[17]

-

-

[18]

0.2 [Cu2 Cr2O5] 3.84(94) [Rh{1}Re{5}/C]

-

[23]

-

[20],[21] ,[22]

2

1.45(72) [Pt{2}/ZrNb PO4] 0.28(72) [Pd/C] 1.7(36) [Pd{0.75} Cs2CO3 {4}/LiAlO2-] 4.8 [Cu/MgO]

4 [Ni]

-

0.75

1

1.92[VOx/Al2O3]

-

-

[17], [24] [19]

0.72

2

1.72 (13.8) [Rh{0.66}–Ir {4}-ReOx{7.8}/ SiO2]

0.42 (3.4) [25] [Rh{0.66}–Ir {4}ReOx{7.8}/ SiO2] Alkanes 0.7 0.95 3 0.67 [Mg-Zr] 0.29(7.3) 0.45 (15) [26] [Pt{4}/SiO2- [Pd{3}/Al Al2O3] 2O] a Numbers present outside parentheses represent weight hourly space velocity (WHSV) in terms of g/(gcatalyst⋅h) and values inside parentheses represent WHSV in terms of g/(g-active metal⋅h). Catalysts used in the process are represented in brackets and the values in the curly braces represent wt.% of active metal.



Page 20 of 23

Table 2. Simplified cost equations for the preliminary estimation of MSP of a platform chemical derivative

$ A = BC + EC + FC + GC + H ?@ $ N ℎ ( ) O I880

Heuristics to Guide the Development of Sustainable, Biomass-Derived

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