Process Synthesis and Analysis - ACS Publications - American

Research Article pubs.acs.org/journal/ascecg

Conversion of Furfural to 1,5-Pentanediol: Process Synthesis and Analysis Kefeng Huang, Zachary J. Brentzel, Kevin J. Barnett, James A. Dumesic, George W. Huber, and Christos T. Maravelias* Department of Chemical and Biological Engineering, University of WisconsinMadison, 1415 Engineering Drive, Madison, Wisconsin 53706, United States S Supporting Information *

ABSTRACT: A new process for the production of 1,5pentanediol (1,5-PDO) from biomass-derived furfural is studied. In this process, furfural is converted to 1,5-PDO in a high overall yield (80%) over inexpensive catalysts via multiple steps involving hydrogenation, dehydration, hydration, and hydrogenation subsequently. To effectively recycle H2 as well as recover 1,5-PDO, detailed separation subsystems have been designed and integrated with reaction subsystems. Furthermore, a pioneer plant analysis is performed to estimate the risk on the cost growth and plant performance shortfalls. The integrated process leads to a minimum selling price of $1973 ton−1 for 1,5PDO, which suggests that it could be a promising approach for converting biomass into oxygenated commodity chemicals, which are difficult to produce from petroleum-derived feedstocks. The sensitivity analysis also identifies that the most important economic parameters for the process include the furfural feedstock price and plant size. KEYWORDS: Biorefinery, 1,5-Pentanediol, Furfural, Catalytic conversion, Process design, Pioneer plant analysis, Technoeconomic analysis

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converted to 1,5-PDO.4−11 1,5-PDO can be potentially used as a direct replacement for 1,6-HDO or 1,4-BDO in several applications (e.g., polycarbonate diol, urethane, and polyetherpolyol). 1,6-HDO and 1,4-BDO have larger market volumes of 138 000 and 2 500 000 tons per year, respectively.12 These markets are projected to grow at a rate of nearly 5% per year. Furfural is one of the most widely produced platform chemicals from biomass. It is manufactured via hydrolysis of hemicellulose to xylose followed by cyclodehydration of xylose.13−15 All major furfural producers use agriculture residues as feedstocks such as corncobs and bagasse with average furfural yields (dry basis) of 10−12 and 8−11%, respectively.16 The production of furfural from fossil-based raw materials (e.g., via the catalytic oxidation of 1,3-dienes) is not economically competitive.17 The furfural market volume is projected to be 490 000 tons per year with an estimated annual growth rate of 4.3%, while its price has been in the range of $900−1000 per ton.16 New technologies are being developed to produce furfural at 4 times lower cost with 3−5 times lower energy consumption, which could dramatically reduce the price of furfural.13,18

INTRODUCTION Lignocellulosic biomass is an abundant and sustainable feedstock that can be used to produce biofuels and bioproducts. The United States has the capacity to sustainably produce 1.2 billion tons of nonfood biomass annually under the base case scenario and 1.5 billion tons under a high-yield scenario by 2040.1 However, the low price of crude oil and the challenges in applying biorefinery technologies at scale hamper the commercial production of biofuels from biomass.2 Another option for biorefineries to become more profitable is to produce high-value commodity chemicals that are expensive to synthesize from petroleum-derived feedstocks. α,ω-Diols, like 1,4-butanediol (1,4-BDO) and 1,6-hexanediol (1,6-HDO), are such chemicals with projected market prices of $1600−2800 and $2500−4500 ton−1, respectively. These α,ω-diols are widely used for industrial polyester, elastic fiber, and polyurethane production. 1,5-Pentanediol (1,5-PDO) can be an alternative to these conventional α,ω-diols because of analogous molecular structure and physical properties such as a relatively low viscosity and glass transition temperature and good flexibility as a building block in the production of polyesters, thermoplastic polyurethanes, and plasticizers.3 The current world capacity of 1,5-PDO is about 3000 tons per year3 due to limited readily accessible C5 petroleum feedstocks. However, C5 platform chemicals from biomass, such as furfural and xylose, have been produced at industrial scale and can be © 2017 American Chemical Society

Received: January 6, 2017 Revised: April 4, 2017 Published: April 17, 2017 4699

DOI: 10.1021/acssuschemeng.7b00059 ACS Sustainable Chem. Eng. 2017, 5, 4699−4706

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ACS Sustainable Chemistry & Engineering

Figure 1. Process flowsheet for the integrated strategy.

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Previous studies have demonstrated that noble metal catalysts are highly selective for the synthesis of 1,5-PDO from furfural and tetrahydrofurfuryl alcohol (THFA).4−9 Tomishige and co-workers have achieved a 94% yield of 1,5PDO from THFA using a Rh−ReOx/C catalyst,5 a 71.4% yield of 1,5-PDO from furfural using a Pd−Ir−ReOx/SiO2 catalyst,9 and a 78.2% yield of 1,5-PDO from furfural using a Rh−Ir− ReOx/SiO2 catalyst.8 These methods all utilize expensive noble metals with relatively low catalytic activities. Brentzel et al.11 have recently reported a new approach to convert furfural into 1,5-PDO in a process that involves hydrogenation and dehydration−hydration−hydrogenation, which we will call DHH later in the paper. First, furfural is hydrogenated into THFA over Pd-, Cu-, or Ni-based catalysts.19−27 Then, THFA is converted into 1,5-PDO at high yields in a three-step process, which eliminates the requirement of a homogeneous or heterogeneous acid catalyst for DHP hydration and the additional neutralization and distillation steps. Thus, the 1,5PDO yield increases from 70 to 86%, compared against the three-step process using DHP and 5-hydroxyvaleraldhyde (5HY-Val) as intermediates.10 Furthermore, the DHH strategy can potentially produce 1,5-PDO from furfural-derived THFA at significantly lower capital and operating costs compared to the previously reported direct hydrogenolysis approach6 for the conversion of THFA into 1,5-PDO.11 A systems-level analysis is required to better understand the economics of the DHH strategy using commercially available furfural as feedstock. The objective of this paper is to study the DHH process for the conversion of furfural into 1,5-PDO, including detailed reaction and separation subsystems, develop a process simulation model based on experimental data, and perform technoeconomic analysis of this new process. We will identify the key economic parameters and suggest future research directions that will minimize the cost of this technology.

METHODS

Process Synthesis, Modeling, and Simulation. We use process systems engineering methods (process modeling, synthesis, and analysis) to assess the economic feasibility of the proposed strategy as well as identify areas where further technology improvements are needed.28−30 The process reported herein combines two conversion subsystems for the (1) hydrogenation of furfural to THFA and (2) three-step conversion of THFA into 1,5-PDO, as well as subsystems for the separation of (1) hydrogen, to be recycled back to the hydrogenation reactors, (2) THFA from byproducts and produced water, and (3) 1,5-PDO from water and byproducts. Figure 1 shows a process flow diagram of the synthesized process for the conversion of biomass-derived furfural to liquid 1,5-PDO. The five main blocks are (1) furfural hydrogenation, (2) THFA purification, (3) 1,5-PDO production, (4) 1,5-PDO recovery, and (5) wastewater treatment. The material balances for this process are reported in Table S1 in the Supporting Information. Furfural Hydrogenation. THFA is made commercially from furfural by hydrogenation of furfural with a nickel-based catalyst or using a mixture of nickel with a copper chromite catalyst.15,19 In this paper, we use vapor-phase furfural hydrogenation. The reaction data for gas-phase hydrogenation of furfural to THFA are taken from the work of Nakagawa et al.,24 who obtained a 94% molar yield of THFA over a Ni/SiO2 catalyst (reaction 1 in Table 1) at 413 K. On the basis of this result, we modeled a catalytic reactor (R-1 in Figure 1) for gasphase hydrogenation in a H2-rich environment (stream 2) with a H2/ furfural molar ratio of 6 (i.e., two times the stoichiometric ratio) in a packed column (D-1), which is heated by steam to evaporate the furfural feed and maintain the temperature at 393 K.15 The resulting vapor mixture of hydrogen and furfural (stream 3) is superheated to the reaction temperature (413 K). We assume that the lifetime of the catalyst is 240 h on stream, which is typical for vapor-phase hydrogenation of furfural to furfuryl alcohol.15 To maintain catalyst activity, the temperature of the hydrogenation reactor is gradually increased to compensate for a progressing decrease in catalyst activity due to carbonaceous deposits. After 240 h, the reactor is shut down and heated to remove the deposits by oxidation, while the feed is switched to the other parallel reactor. Then, the catalyst is reactivated by hydrogenation before a new production cycle begins.15 When 4700


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ACS Sustainable Chemistry & Engineering Table 1. Summary of Reactions and Laboratory Yields

a

Residence time is defined based on the mass of total solution.

designing the subsequent catalytic steps, two parallel units are employed for each step to maintain continuous operation. The cost of the two reactors is included in the total installed equipment cost. THFA Purification. The gaseous mixture of hydrogenation products (stream 4) enters a condensation unit comprising a packed column (D-2), a pump, and a cooler. The pump circulates raw THFA through the cooler and into D-2 where it meets a countercurrent stream of the gaseous products. The top vapor fraction (stream 5), consisting of unreacted H2 and small amounts of condensables, is recompressed via the H2 recycle compressor (C-1) and added to the H2 feed to prevent losses. A 5.0%31 fraction of the recycled gas is purged to mitigate buildup of impurities and produce process heat and electricity in the boiler/turbogenerator if necessary. The condensed portion (stream 7) is fed into the reboiler of a vacuum distillation system (D-3) to obtain purified THFA from the sump fraction for the subsequent process block (1,5-PDO production), while a small head fraction (stream 8), mainly consisting of 2-methyltetrahydrofuran (2-MeTHF) and reaction water from the 2-MeTHF formation, is sent to the wastewater treatment block. In practice, high-boiling polymers remaining in the reboiler of D-3 are withdrawn intermittently. We assume that 98.5% of THFA is recovered through this purification block. 1,5-PDO Production. THFA (stream 9) is dehydrated in the gas phase (R-2) at 648 K and 1 bar to produce dihydropyran (DHP) over a γ-Al2O3 catalyst. The DHP product (stream 10) is then diluted in the buffer tank (T-1) using process water from the wastewater treatment block. This liquid mixture (stream 11) is hydrated to 2hydroxytetrahydropyran (2-HY-THP), 5-tetrahydropyranyloxy-pentanal (THP-oxypentanal), and 2-tetrahydropyranyl ether (2,2′-HY-

THP) at 90.2, 7.1, and 1.3% molar yields, respectively, in a mixture of 20 wt % DHP with water at 403 K in the hydration reactor (R-3). DHP has low water solubility (16 g/L water at room temperature), while the resulting hydration products have high water solubility (146 g/L at room temperature). The resulting aqueous 2-HY-THP-rich stream (stream 12) is fed to the hydrogenation reactor (R-4), at 66 bar and 393 K, to produce 1,5-PDO in a H2-rich environment (a H2/2HY-THP feed molar ratio = 16 is currently used in our experiment) over Ru/C at a 97.5% molar yield (reaction 6 in Table 1). THPoxypentanal and 2,2′-HY-THP are also converted to 1,5-PDO at 97.5 and 97.5% molar yields, respectively (reactions 7 and 8 in Table 1). 1,5-PDO Recovery. Following the conversion of 1,5-PDO, most of H2 remaining in the product stream (stream 14) is recovered by a vapor−liquid flash drum (F-1), wherein 98.9% of H2 is recovered from the product stream and recompressed (C-3) back to the hydrogenation reactor (R-4). The remaining product stream (stream 16) is depressurized in the subsequent flash drum (F-2), a relatively small quantity of H2 thereby being vented into the ambient air. The depressurized liquid (stream 17), containing 23.7 wt % of 1,5-PDO, is sent directly to the fraction column (D-4) for purification. 1,5-PDO (99.0 wt %) is obtained at the bottom of D-4 at 482 K and 0.4 bar. The 1,5-PDO product is further cooled to 343 K and pumped to product storage (stream 19). The distillation top liquid (stream 18), mainly consisting of the produced water and other trace byproducts, is sent to the wastewater treatment block. Wastewater Treatment. All of the wastewater generated in the process is sent to the wastewater treatment block. Assuming that the treated water is fully reusable and that the wastewater treatment block 4701


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ACS Sustainable Chemistry & Engineering has an overall 2.2% loss,31 the recovered water is 376 kg/h more than the water required in the process, which means that the water requirement for DHP hydration in the 1,5-PDO production block is met using recycled water. The wastewater treatment block includes anaerobic digestion, aerobic digestion, sludge dewatering, reverse osmosis, evaporation, and centrifugation.31 This design allows us to adjust the individual unit costs based on the hydraulic flow rate or chemical oxygen demand (COD) from the simulation results, thus resulting in improved cost estimation accuracy (e.g., to accommodate differences in COD concentration even at a similar total hydraulic flow rate). Design Basis and Assumptions. On the basis of the experimental data and simulation results, the size and cost of all of the units in four blocks (furfural hydrogenation, THFA purification, 1,5-PDO production, and 1,5-PDO recovery) were estimated using Aspen Process Economic Analyzer (V8.8 Aspen Technology). Detailed cost information on major equipment units is listed in Table S2 in the Supporting Information. The equipment cost of the wastewater treatment block was estimated using an exponential scaling expression based on COD and hydraulic load for the equipment size and cost data in the NREL’s design.31 The feedstock processing rate is 5100 kg/h of furfural, which is estimated to be equivalent to 1000 dry tons of white birch per day. This furfural feed rate is equivalent to 8.0% of its 2019 projected production. The total annual 1,5-PDO production is 37 000 tons, which will result in 25% of the 2019 projected market of 1,6-HDO if 1,5-PDO is considered to be a substitute for 1,6-HDO. If 1,5-PDO can be produced at a cost comparable to 1,4-BDO, its substitution merely accounts for 1.5% of the 2019 projected market of 1,4-BDO. Therefore, the markets are projected to be able to handle the proposed feed and production rates. All equipment cost is indexed to year 2015 using the Chemical Engineering’s Plant Cost Index.32 The utilities (including electricity, steam, and cooling water), as well as H2, are assumed to be available for purchase at the prices shown in Table 2.

Table 3. Capital and Operating Costs for an nth Plant and Pioneer Plant Producing 37 000 tons of 1,5-PDO Annually process block furfural hydrogenation THFA purification 1,5-PDO production 1,5-PDO recovery wastewater treatment OSBLa (storage etc.) total installed equipment cost total (nth plant) total (pioneer plant) raw material feedstock H2 makeup catalyst reprocessing other raw materials heating steams cooling utilities electricity fixed costs (nth plant) fixed costs (pioneer plant) total (nth plant) total (pioneer plant) a

OSBL (outside battery limits of the plant) considers on-site bulk storage for furfural feed, 1,5-PDO product, and process chemicals.

biomass plant31 and other overhead costs, including maintenance and property insurance, are calculated based on the capital cost. A pioneer plant analysis33 was carried out to estimate the cost growth and plant performance shortfalls associated with the construction and operation of such a first-of-kind plant to appropriately account for the risk associated with developing a pioneer process. The methodology is developed based on statistical regressions of industrial data for plant performance and cost growth, which are estimated using the parameters and equations from Table 4. The industrial data for plant performance suggest that if plant performance fails to reach 40% capacity after year 1 with a 20% annual increase from the beginning, it is unlikely to achieve nameplate capacity without a significant capital investment. However, this pioneer plant analysis indicates that the proposed process would reach 46% capacity after year 1 and full capacity after 6 years. The cost growth analysis suggests that the total capital investment for a pioneer plant would be 2.1 times ($106.2 million yr−1; see Table 3) compared to an nth plant. The total operating cost from the pioneer plant analysis ($56.3 million yr−1) is slightly higher than that from the nth plant analysis ($56.0 million yr−1) because the fixed operating costs are calculated based on the total capital costs. Minimum Selling Price. The minimum selling price (MSP) of 1,5-PDO (i.e., the price that leads to zero net present value) was calculated based on the capital and operating costs (Table 5) calculated using the economic parameters, assumptions, and discounted cash flow methodology (Table S4 in the Supporting Information) used by NREL.31 The sensitivity of the MSP to the percentage of equity financing and the after-tax discount rate (IRR) is illustrated in Figure S1 in the Supporting Information. Although the total capital investment for the pioneer plant is 2.1 times higher than that of the nth plant, the MSP of 1,5-PDO for the pioneer plant

Table 2. Baseline Feedstock Costs, Utility Costs, and Other Assumptions Used in This Study furfural purchase price ($/ton)a hydrogen purchase price ($/ton)b high-pressure steam ($/kJ)c low-pressure steam ($/kJ)c cooling water purchase price ($/kJ)d electricity purchase price ($/kWh)b plant operating hours per year (hours)b

capital cost (MM$) 1.9 1.1 4.6 4.4 9.0 1.2 22.3 49.6 106.2 operating cost (MM$/year) 44.3 4.8 0.5 0.1 1.7 0.2 0.9 3.5 3.9 56.0 56.3

1000 1263 5.310 × 10−6 3.260 × 10−6 3.540 × 10−7 0.069 7884

a

Taken from a report by IHS.16 bTaken from a study by NREL.31 Estimated from a report by DOE.34 dEstimated using Aspen Process Economic Analyzer (V8.8 Aspen Technology). c

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RESULTS AND DISCUSSION Capital and Operating Costs. The capital costs of all process blocks are shown in Table 3. The total installed equipment cost is estimated to be $22.3 million, whereas the total capital investment, which includes other direct (warehouse, site development, and additional piping) and indirect (e.g., project contingency, construction, field expense, and engineering) costs, is $46.3 million. It should be noted that a relatively high project contingency (40%) is used. The total operating cost is estimated to be $56.0 million yr−1, as shown in Table 3, and the feedstock cost is the most significant component (79.1% of the total operating cost). The fixed operating cost (e.g., labor, supervision, maintenance, and insurance costs) is $3.5 million yr−1. Labor and supervision costs are fixed based on the number of employees and associated salaries recommended by the NREL’s report for a 4702


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ACS Sustainable Chemistry & Engineering Table 4. Pioneer Plant Analysis Parameters and Equationsa parameters plant performanceb NEWSTEPS BALEQS WASTE SOLIDS cost growthc PCTNEW IMPURITIES COMPLEXITY INCLUSIVENESS PROJECT DEFINITION

definition number of new process steps (block basis) percentage of heat and mass balance equations based on actual prior plant data waste disposal factor factor for the presence of solids estimate (%) of unproven technology incorporated in commercial use factor for impurities present in the process block count of all process steps in plant percentage of land purchase, initial inventory, preoperating personal included in analysis levels of site-specific information and engineering included in estimate

range

value

0−86 ≥0

39 4

0−100

0

0−5 0 or 1 >0 0−100

2 0 0.46 26

0−5

5

≥1

7

0−100

100

2−8

8

($1973 ton−1) is only $308 per ton higher than the nth plant ($1665 ton−1) because the operating cost is the primary cost driver. The subsequent discussion is based on only the pioneer plant analysis to avoid routinely overstating any advantages. Figure 2 shows the carbon flow per process block if the 1,5PDO production block is further spilt into three sub-blocks: THFA dehydration, DHP hydration, and 2-HY-THP hydrogenation. The overall carbon yield from furfural to 1,5-PDO is 80% (20% of carbon is lost as a byproduct in the wastewater treatment block and coke). Figure 2 also shows the contribution to the MSP by the process block. The feedstock cost (furfural at $1000 ton−1) is the highest contributor ($1177 ton−1, 59.6%), while the wastewater treatment block is the second highest contributor ($242 ton−1, 12.3%). The next highest cost driver, contributing $155 ton−1 or 7.9% to the overall MSP, is the 1,5-PDO recovery block due to primarily the capital and operating expenses associated with the 1,5-PDO purification operation via distillation. The furfural hydrogenation block is also a significant cost contributor due to the purchased H2 cost ($104 ton−1). However, the 2-HY-THP hydrogenation block has a 2.7 times smaller variable operating cost than the furfural hydrogenation block because stoichiometrically furfural hydrogenation requires 3 times more H2 than 2-HY-THP hydrogenation. Sensitivity Analysis. Each variable is changed to a reasonable maximum and/or minimum value with all other factors held constant (see Figure 3; ΔMSP represents the deviation of the corresponding MSP from the base case MSP). The feedstock cost is the dominant expense. When the furfural purchase price increased or decreased by $100 from $1000 ton−1 (base case scenario), the MSP varied by nearly 6.0%. While the single-point sensitivity to the furfural price is intended to capture a reasonable range of expected costs (based on U.S. furfural price fluctuations over recent years), larger changes are considered, as shown in Figure 4. This analysis demonstrates that the MSP of 1,5-PDO can range from $1400 to $3200 if the furfural purchase prices fluctuate between $500 and $2000 per ton,16 as they have over the past 15 years. Because the furfural price is stable around $1000 ton−1 in recent years (base case), 1,5-PDO produced from the proposed

a

Other equations and assumptions are listed in Table S3 in the Supporting Information. bPlant performance = 85.77 − 9.69 × NEWSTEPS + 0.33 × BALEQS − 4.12 × WASTE − 17.91 × SOLIDS. cCost growth = 1.1219 − 0.00297 × PCTNEW − 0.02125 × IMPURITIES − 0.01137 × COMPLEXITY + 0.00111 × INCLUSIVENESS − 0.06361 × PROJECT DEFINITION.

Table 5. Comparison of Costs and Revenues Between the nth Plant and Pioneer Plant ($/ton 1,5-PDO) nth plant revenues operating capital depreciation average income tax average ROIa 1,5-PDO sales a

pioneer plant costs

revenues

1486 41 24 114 1665

costs 1496 89 73 316

1973

ROI: return on investment.

Figure 2. Cost contribution per process block ($/ton 1,5-PDO) based on pioneer plant analysis. The total cost ($1973/ton) includes also OSBL (capital = $25/ton; fixed operating = $6/ton). 4703


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Figure 3. Single-point sensitivity tornado chart for the key economic/process parameters based on pioneer plant analysis.

volume of 1,5-PDO, the MSP of 1,5-PDO increases to $3867 ton−1, which may not be cost-competitive with 1,6-HDO. This suggests that a comprehensive investigation is required for the applications of 1,5-PDO as a substitute for 1,6-HDO and 1,4BDO. Ultimately, increasing the supply of 1,5-PDO would decrease its market price. For instance, a large plant with annual production of 50 000 tons would decrease the MSP of 1,5-PDO to $1900 ton−1 (see Figure 5), which is cost-competitive with 1,4-BDO. This supply rate accounts for merely 2.0% of the 2019 projected market of 1,4-BDO if 1,5-PDO is considered to be a substitute for 1,4-BDO. The DHP loading in H2O can also have a big impact. If no additional process water is added to the DHP hydration reactor, the DHP concentration can be as high as 76 wt %, which leads to (1) smaller flows of H2O moving through the process, which in turn leads to decreased capital investment, and (2) lower energy requirements for the separation of H2O from 1,5-PDO (distillation). Thus, it could decrease the MSP of 1,5-PDO to $1654 ton−1. However, the steam utility cost for separation is low ($39.2 ton−1) because a relatively high DHP loading (20 wt %) is achieved. Finally, the price of H2 plays an important role due to the large amount of H2 required for the hydrogenation of furfural and 2-HY-THP. If hydrogen is sourced externally via off-site natural gas steam-methane reforming,31 then its cost will depend on the price of natural gas ($0.5−20 MMBtu−1) as well as the transportation cost, which in turn depends on both transportation distance and mode (e.g., pipeline vs tube trailer). Thus, a large hydrogen cost range ($1.0−4.0 kg−1) is considered. However, a nearly 3 times increase of H2 purchase price merely leads to an increase of more than $200 in the MSP because effective separation subsystems have been integrated to recover and recycle the excessive H2. This also explains why the H2 to reactant (furfural and 2-HY-THP) feed molar ratios have limited impact on the overall cost, as shown in Figure 3. Furthermore, the overall product yield plays a less critical role because it is already 80% in the base case. When the product yield increases from 80 to 85%, the MSP decreases by 5.9%. Catalyst stability plays a limited role because inexpensive catalysts are employed.

Figure 4. MSP of 1,5-PDO as a function of furfural price based on pioneer plant analysis.

process is cost-competitive with 1,4-BDO and it also provides a potential economically viable substitute for 1,6-HDO (see market prices of 1,4-BDO and 1,6-HDO in Figure 4). Additionally, plant size and capital cost also weigh heavily on costs. Figure 5 illustrates the MSP of 1,5-PDO as a function of plant size. If a relatively small plant is built with an annual production scale of 3000 tons, which is the current market

Figure 5. MSP of the 1,5-PDO sensitivity scan as a function of plant size based on pioneer plant analysis. 4704


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tetrahydrofurfuryl alcohol to 1,5-pentanediol over Rh/SiO2. J. Catal. 2009, 267 (1), 89−92. (5) Chen, K.; Koso, S.; Kubota, T.; Nakagawa, Y.; Tomishige, K. Chemoselective Hydrogenolysis of Tetrahydropyran-2-methanol to 1,6-Hexanediol over Rhenium-Modified Carbon-Supported Rhodium Catalysts. ChemCatChem 2010, 2 (5), 547−555. (6) Chia, M.; Pagán-Torres, Y. J.; Hibbitts, D.; Tan, Q.; Pham, H. N.; Datye, A. K.; Neurock, M.; Davis, R. J.; Dumesic, J. A. Selective Hydrogenolysis of Polyols and Cyclic Ethers over Bifunctional Surface Sites on Rhodium−Rhenium Catalysts. J. Am. Chem. Soc. 2011, 133 (32), 12675−12689. (7) Nakagawa, Y.; Tomishige, K. Production of 1,5-pentanediol from biomass via furfural and tetrahydrofurfuryl alcohol. Catal. Today 2012, 195 (1), 136−143. (8) Liu, S.; Amada, Y.; Tamura, M.; Nakagawa, Y.; Tomishige, K. Performance and characterization of rhenium- modified Rh−Ir alloy catalyst for one-pot conversion of furfural into 1,5-pentanediol. Catal. Sci. Technol. 2014, 4 (8), 2535−2549. (9) Liu, S.; Amada, Y.; Tamura, M.; Nakagawa, Y.; Tomishige, K. One-pot selective conversion of furfural into 1,5-pentanediol over a Pd-added Ir−ReOx/SiO2 bifunctional catalyst. Green Chem. 2014, 16 (2), 617. (10) Schniepp, L. E.; Geller, H. H. Preparation of Dihydropyran, δHydroxyvaleraldehyde and 1,5-Pentanediol from Tetrahydrofurfuryl Alcohol. J. Am. Chem. Soc. 1946, 68 (8), 1646−1648. (11) Brentzel, Z. J.; Barnett, K. J.; Huang, K.; Maravelias, C. T.; Dumesic, J. A.; Huber, G. W. Chemicals from Biomass: Combining Ring-opening Tautomerization and Hydrogenation Reactions to Produce 1,5-Pentanediol from Furfural. ChemSusChem 2017, 10, 1351. (12) MarketsandMarkets. 1,6-Hexanediol Market by Application (Polyurethanes, Coatings, Acrylates, Adhesives, Unsaturated Polyester Resins, Plasticizers, and Others) and By Geography (NA, Europe, AsiaPacific, & ROW) - Trends and Forecasts to 2019; 2014. (13) Xing, R.; Qi, W.; Huber, G. W. Production of furfural and carboxylic acids from waste aqueous hemicellulose solutions from the pulp and paper and cellulosic ethanol industries. Energy Environ. Sci. 2011, 4 (6), 2193−2205. (14) Dashtban, M.; Gilbert, A.; Fatehi, P. Production of Furfural: Overview and Challenges. J. Sci. Technol. Forest Prod. Process. 2012, 2, 44. (15) Zeitsch, K. J. The chemistry and technology of furfural and its many by-proudcts; Elsevier, 2000. (16) IHS Chemical. Furfural - Chemical Economics Handbook; 2016. (17) Mariscal, R.; Maireles-Torres, P.; Ojeda, M.; Sádaba, I.; López Granados, M. Furfural: a renewable and versatile platform molecule for the synthesis of chemicals and fuels. Energy Environ. Sci. 2016, 9 (4), 1144−1189. (18) Wettstein, S. G.; Alonso, D. M.; Gürbüz, E. I.; Dumesic, J. A. A roadmap for conversion of lignocellulosic biomass to chemicals and fuels. Curr. Opin. Curr. Opin. Chem. Eng. 2012, 1 (3), 218−224. (19) Wojcik, B. H. Catalytic Hydrogenation of Furan Compounds. Ind. Eng. Chem. 1948, 40 (2), 210−216. (20) Dunlop, A. P.; Horst, S. Production of tetrahydrofurfuryl alcohol. U.S. Patent US2838523A, 1958. (21) Merat, N.; Godawa, C.; Gaset, A. High selective production of tetrahydrofurfuryl alcohol: Catalytic hydrogenation of furfural and furfuryl alcohol. J. Chem. Technol. Biotechnol. 1990, 48 (2), 145−159. (22) Sitthisa, S.; Sooknoi, T.; Ma, Y.; Balbuena, P. B.; Resasco, D. E. Kinetics and mechanism of hydrogenation of furfural on Cu/SiO2 catalysts. J. Catal. 2011, 277 (1), 1−13. (23) Nakagawa, Y.; Tomishige, K. Total hydrogenation of furan derivatives over silica-supported Ni−Pd alloy catalyst. Catal. Commun. 2010, 12 (3), 154−156. (24) Nakagawa, Y.; Nakazawa, H.; Watanabe, H.; Tomishige, K. Total Hydrogenation of Furfural over a Silica-Supported Nickel Catalyst Prepared by the Reduction of a Nickel Nitrate Precursor. ChemCatChem 2012, 4 (11), 1791−1797.

In summary, our analysis suggests that the two parameters that appear to be the most important are the furfural feedstock price and plant size. Thus, a large market for 1,5-PDO (e.g., 50 000 tons per year) should be established to substitute its application for 1,4-BDO and 1,6-HDO.

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CONCLUSIONS A new 1,5-PDO production process employing multistep catalytic conversions from biomass-derived furfural was developed and analyzed using a rigorous process model. Laboratory data showed that the process has high overall yields while employing inexpensive catalysts. Effective separation subsystems are required for the recycling of H2 and H2O as well as the recovery of 1,5-PDO. Using a pioneer plant analysis, the process leads to a MSP of $1973 ton−1 of 1,5-PDO. Technoeconomic analysis suggested that this process could be a promising approach for converting biomass into oxygenated commodity chemicals that are difficult to produce from petroleum-derived feedstocks.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b00059. Additional information for important stream data and economic evaluation (PDF)

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Tel.: +1 608 265 9026. Fax +1 608 262 5435. ORCID

Kefeng Huang: 0000-0002-3972-6074 Zachary J. Brentzel: 0000-0001-8577-2963 James A. Dumesic: 0000-0001-6542-0856 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was funded by the Department of Energy, Office of Energy Efficiency and Renewable Energy (EERE), under Award Number DE-EE0006878. We thank William F. Banholzer for helpful discussions about α,ω-diols. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the Department of Energy.

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REFERENCES

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