You are on page 1of 8

Research Article

pubs.acs.org/journal/ascecg

Assessment of Biocatalytic Production Parameters to Determine


Economic and Environmental Viability
Sampath Gunukula, Troy Runge, and Robert Anex*
Biological Systems Engineering Department, University of Wisconsin, 460 Henry mall, Madison, Wisconsin 53706, United States
*
S Supporting Information

ABSTRACT: The minimum selling price (MSP), specic energy consumption,


and greenhouse (GHG) emissions resulting from biobased production of adipic
acid, succinic acid, 1,3-propanediol, 3-hydroxy propionic acid, and isobutanol
were estimated for various combinations of titer, yield, and volumetric
productivity. The MSP, energy consumption, and GHG emissions of anaerobic
biobased commodity chemical processes were found to be nearly the same for a
given titer, yield, and productivity. The estimated MSP of biobased commodity
chemicals produced via aerobic respiration was found to be nearly 30% higher
than those of produced through anaerobic fermentation. It was determined that
biocatalyst yields of 0.32 g/g and titers of 45 g/L result in lower production
cost, energy consumption, and GHG emissions, when compared to conventional petrochemical production processes. The
economic and environmental benets of improving titer beyond 125 g/L and volumetric productivity beyond 2 g/Lh were
found to be low when producing biobased commodity chemicals using a biocatalyst. Comparative economic analysis indicated
that provision of feedstock is the dominant cost in commercially viable biobased commodity chemical production systems.
KEYWORDS: Sustainability, Renewable chemicals, Biofuels, Techno-economic analysis, Life cycle analysis, Biomass valorization

INTRODUCTION
The depletion of fossil feedstocks, economic and market risks
Typically, inherent trade-os exist among biocatalyst yield,
titer, and production rates. For example, lower fermentation
yields may be oset by achieving higher production rates and
to investments, and growing concern over global warming
vice versa. Determining such trade-os is necessary to guide
impacts are driving interest in the development of new
biocatalyst technology development by setting performance
technologies for the conversion of agricultural and forestry
targets to the technology development team.79 The aim of this
materials to fuels and chemicals.14 One way to convert such work is to determine the existence of generalities in the area of
biobased feedstocks to valuable products is using biocatalysts.5 biobased commodity chemical production, which can be used
Advances in the elds of synthetic biology and metabolic by technology development teams to quickly assess the
engineering have made it possible to modify microbial economic potential and environmental sustainability of early
metabolism to develop ecient industrial biocatalysts that are stage biocatalytic technologies as well as to guide the
used to make commodity chemicals and fuels from biobased development of these new technologies.
feedstocks. Signicant investment has been made by both In this work, we analyzed the economic and environmental
government and industry in research and development (R&D) performance of a range of biobased commodity chemical
of new biocatalytic technologies for the conversion of biobased production processes that were chosen to be representative of a
feedstocks to fuels and chemicals. Many of these investments wide range of such production processes to determine if general
have incurred losses and, so far, few technologies have been trends in the area of biobased commodity chemical production
commercialized.6 exist. Criteria including nature of cultivation (aerobic/
To avoid potential losses to R&D investments, it is necessary anaerobic), the type of product separation and purication
to screen early stage biocatalytic technologies before large processes, and the availability of data for the process
investments are made and to ensure the technologies developed simulations were considered while selecting the range of
are environmentally benign. Development of environmentally biobased commodity chemical production processes. Speci-
benign biocatalytic technologies is necessary to reduce GHG cally, the economic and environmental potential of processes
emissions of chemical and fuel industry. Assessing the for the biocatalytic production of succinic acid, adipic acid,
economic and environmental potential of new biocatalytic isobutanol, 1,3-propanediol, and 3-hydroxy propionic acid (3-
technologies requires expertise of process modeling, techno- HPA) were determined and used for this analysis.
economic analysis (TEA), and life cycle analysis (LCA).7 Often,
the biocatalyst development teams do not have expertise in Received: May 31, 2017
these areas and such assessments require considerable resource Revised: July 18, 2017
investment. Published: July 23, 2017

XXXX American Chemical Society A DOI: 10.1021/acssuschemeng.7b01729


ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

Table 1. Model Molecules for Analyzing Multiple Microbial Pathways Using the Feasible Space Approach
biobased commodity chemical resistance to pHa type of separation type of cultivation theoretical yield (g/g)b [source]
succinic acid high (23) distillation anaerobic/ 0.57 [32]
microaerobic
adipic acid low (57) distillation anaerobic 0.52 [29]
isobutanol high (79) distillation anaerobic 0.35 [33]
1,3-propanediol high (79) LLEc microaerobic 0.51 [35]
1,3-propanediol high (79) LLE aerobic 0.34 [34]
3-HPA medium (45) LLE anaerobic 0.60 [30]
3-HPA medium (45) LLE microaerobic 0.55 [31]
a
Values in the parentheses represent the desired pH during the production of biocommodity chemicals. bAll these products are growth-associated
products. Above theoretical yields are computed at the specic growth rate of 0.1 g biomass/g glucoseh. cLiquid-Liquid Extraction.

The GHG emissions (g CO2 equiv/kg), energy consumption After the cell clarication step, adsorption, distillation, or solvent
(MJ/kg), and the MSP ($/kg) of analyzed biobased extraction processes can be used to extract a product from the claried
commodity chemical production processes were found to be culture media.15 The low capacity and troublesome solids handling of
adsorption process made this process not suitable for the extraction of
nearly same for a given combination of titer, yield, and
a product from the claried culture media.19 In the third and nal step,
productivity. However, these performance metrics did vary with the product is puried using processes such as crystallization or ion-
the nature of cultivation (aerobic/anaerobic). General cost, exchange.16 Among the three separation and purication process steps,
energy, and GHG contour plots were created for the aerobic the second step dominates the total separations cost, energy
and anaerobic/micro-aerobic production of biobased commod- consumption, and GHG emissions. This is due to the fact that energy
ity chemicals, and these plots can be used to determine consumption and operating costs of a separation unit process are
economic and environmental feasibility. The results of the plots directly related to the volume of a feed from which the product is
can also serve as a guide in the development of new processes extracted.16
Processes with intracellular chemical production require two
to produce biobased commodity chemicals using biocatalysts.

additional process steps after separating the cellular material from


the culture media. The rst additional step involves lysing microbial
METHODOLOGY cells to extract the product, and in the second step cell debris are
Criteria for the Selection of Chemicals. In this study, we removed.16 A homogenization process can be used for lysing microbial
selected multiple biobased commodity chemical processes that meet cells, and a membrane ltration process is used to remove the cell
debris.16 The increase in capital and operating costs due to the
the following criteria of process characteristics: aerobic/anaerobic/
addition of homogenization and membrane ltration processes could
microaerobic, extracellular product formation, biocatalyst resistance to
make intracellular product accumulation economically unattractive for
pH changes, and distillation/solvent processes for the extraction of a
biobased commodity chemical production. Unfortunately a lack of
product from the claried culture media (Table 1). For the detailed
type and concentration of cellular material data have prevented us
description of the metabolic route for each of these chemicals listed in
from testing this hypothesis in this analysis.
Table 1, please refer to the Supporting Information. The criteria for
Process Flow Diagram (PFD) of Biocommodity Chemical
the selection of a range of biobased commodity chemical processes Production. We created PFDs to produce biobased commodity
were determined by considering major process steps that inuence the chemicals listed in the Table 1 using information obtained from the
economic and environmental performance of biobased commodity patents and published articles (Figures S1S3). The major process
chemical production. The major process steps of a biobased sections of a PFD are the production of sugar from corn through dry-
commodity chemical production using a biocatalyst include feedstock mill process, conversion of sugar to the biobased commodity chemical,
production, conversion of a feedstock to the chemical in a bioreactor, separation and purication of biobased commodity chemical, and the
and the separation and purication of the chemical.10,11 production of dried distillers grains with solubles (DDGS). The
The contribution of feedstock cost, energy consumption, and the biobased commodity chemical production plant was assumed to be
GHG emissions to the total production cost, energy consumption, and located in the Midwest region of United States. The sugar was
GHG emissions of a process for the production of a biobased assumed to be derived from corn, as it is produced abundantly in the
commodity chemical are directly related to the process parameter Midwest. We obtained modeling parameters to produce sugar and
yield.12 The amount of an acid or base added to the bioreactor to DDGS from Kwiatkowski et al.20 The detailed description of PFDs
maintain pH of the cultivation process is one of the factors aecting and the modeling parameters of biobased commodity chemical
the cost of a cultivation media. The addition of acid or base to a media production are provided in the Supporting Information on this paper.
can be minimized by developing a biocatalyst that is tolerant to a wide We assumed the nth plant of its kind for the plant design, and
range of pH values.13 The bioreactor cost is a function of volumetric therefore, did not account special costs associated with the rst of a
productivity (process parameter) and the type of a cultivation process kind plants. The annual plant capacity of 150 000 MT of corn
(aerobic/anaerobic/microaerobic).14 conversion to a biobased commodity chemical, the plant life of 20
The total cost, energy consumption, and GHG emissions of years, and the annual operating days of 330 were assumed.
separation and purication processes used for the extraction of a Estimation of Capital and Operating Costs. Each chemical
chemical from the cultivation broth are driven by titer (process production process was modeled using the SuperPro Designer
parameter), nature of a product accumulation (intracellular/extrac- simulation software. The costs of standard equipment (distillation,
ellular), and the type and number of unit processes used for the evaporators, and heat exchangers) were estimated using purchase-cost
extraction of a product after aerobic/anaerobic/microaerobic culti- charts.21,22 The costs of aerobic vessel, microaerobic vessel, anaerobic
vation.15 In the case of extracellular chemical production, the rst step fermentor, and seed reactors were determined from vendor quotes and
of the downstream processing involves separation of microbial cells a personal communication with consulting rms. The costs of
from the culture media.16 However, a cell clarication step is not equipment used in the corn dry grind process and DDGS dryer
required in the production of few biobased commodity chemicals. For were obtained from Kwiatkowski et al.,20 and the six-tenths rule was
instance, culture broths containing isobutanol and ethanol are directly employed to calculate the cost of a required size. The total capital
sent to a distillation column after the fermentation process.17,18 investment of chemical production plant was estimated using a

B DOI: 10.1021/acssuschemeng.7b01729
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

method based on delivered cost of process equipment.22 Capital costs and productivity. But, for a particular fermentation yield only a
of biocommodity chemical production plants will be dierent for 200% increase in MSP is noticed when the titer is reduced to 10
dierent titers and productivities. A combination of titer of 100 g/L from 200 g/L. The high eect of yield is mainly because the
and productivity of 2 g/Lh has been chosen to represent capital costs entire upstream of biobased commodity chemical production
of biocommodity chemical production processes. These numbers will
provide a general idea of the capital costs associated with the (including production of corn, production of glucose from corn
production of biocommodity chemicals. The total capital costs ($ using the dry grind process, and the production of a chemical
MM) associated with the production of adipic acid, succinic acid, 1,3- from glucose in a bio reactor) are aected by any variation in
propanediol (microaerobic conditions), 1,3-propanediol (aerobic the fermentation yield value.
conditions), 3-HPA (microaerobic conditions), 3-HPA (anaerobic The MSP of biobased commodity chemicals, except those
conditions), and isobutanol are 149, 151, 134, 272, 145, 139, 137, produced aerobically, is found to be nearly constant for a given
respectively. titer, yield, and productivity. For example, the calculated MSP
The material and energy balances of each chemical production of 1,3-propanediol that is produced under microaerobic
process were obtained from the process simulations. The material
fermentation is 1.13 ($/kg) for the yield of 0.6 g/g, volumetric
balance was used to calculate the required quantity of raw materials,
and the energy balance was utilized to determine steam and electricity productivity of 2 g/Lh, and the titer of 50 g/L (Figure S5). For
requirements. The raw material and utility prices, labor and the same process parameter values, the MSP of aerobically
maintenance costs, and local taxes used in this analysis are listed in produced 1,3-propanediol is estimated at 1.66 ($/kg). Such an
Table S1. The discounted cash ow analysis (DCA) method was used increase of MSP is due to the requirement of high capital and
to compute the biobased commodity chemical MSP. A discount rate of operating costs for the aerobic cultivation as compared to
10% was employed in the DCA.16 anaerobic/microaerobic fermentation. The current available
Estimation of Life Cycle Energy Use and GHG Emissions. The agitator size limits the aerobic reactor volume to 4000 kL.14
cradle-to-gate energy consumption and GHG emissions of biobased The cost advantages due to economies of scale are, therefore,
commodity chemical production processes were calculated using LCA
methodology. The LCA system boundary covers all activities from
minimized for an aerobic reactor, which increases the capital
corn production to the production of a biobased commodity chemical. cost of aerobic cultivation processes. The compressor energy
The functional unit was dened as 1 kg of biocommodity chemical requirements and the energy losses in gassing systems increase
production. The life cycle GHG emissions and energy consumption of the operating costs of aerobic cultivation processes.14
steam, electricity, and corn production processes were obtained from The addition of acid or base to maintain medium or high pH
the Ecoinvent database in SimaPro 7.2 software.23 The 2007 in the production fermentor is found to have negligible impact
Intergovernmental Panel on Climate Change (IPCC) Global Warming on the production cost of biobased commodity chemicals. For
Potentials (GWPs) method was employed to convert GHG emissions example, ammonium hydroxide is added to the fermentor
to CO2 eq emissions. The economic allocation approach was used to
during adipic acid production to maintain the pH around 5.28
partition energy consumption and GHG emissions of biobased
commodity chemical production process among the product and The addition of such base is not necessary for the succinic acid
coproduct DDGS.24 fermentation as the genetically modied yeast strain can make
We calculated MSP, energy consumption, and GHG emissions of succinic acid under low pH conditions.28 However, the
biobased commodity chemical production processes for a wide range estimated production costs of adipic and succinic acids for a
of yield, titer, and volumetric productivity values. The performance given combination of titer, yield, and productivity are nearly the
contour plot for cost was created by mapping biobased commodity same (Figure S6). It should be noted that the salts formed due
chemical MSP to the corresponding yield, titer, and volumetric to the addition of acid or base will end up in the DDGS, and it
productivity. Similarly, performance contour plots for energy and is assumed in this analysis that the presence of salts do not
GHG were created. The energy consumption and GHG emissions of
petroleum based adipic acid, succinic acid, isobutanol, 3-HPA, and 1,3-
aect the market price of DDGS. Please refer to the Supporting
propanediol production processes were obtained from the liter- Information on this paper for the sensitivity analysis if the salt is
ature.25,26 The market prices of these chemicals were obtained from assumed to be a waste stream and the impact that the
ICIS chemicals.27 The performance metrics of conventional processes additional cost of salt waste treatment will have on the MSP of
and performance contour plots were used to determine feasible curves the biocommodity chemical.
of cost, energy, and GHG. The feasible space of each biobased The downstream processing costs of biobased commodity
commodity chemical production process was dened by graphing the chemical production processes are found to be nearly the same
feasible curves of cost, energy, and GHG along with yield, titer, and for a given titer even with dierent number and type of
volumetric productivity constraints. The maximum attainable yield, separation processes. For example, distillation and solvent
titer, and production rates were used to determine yield, titer, and
volumetric productivity constraints, respectively.7 extraction processes are used to extract isobutanol and 3-HPA

from the culture media, respectively. Moreover, the total


number of unit processes for the purication of isobutanol is
RESULTS AND DISCUSSION low compared to the purication of 3-HPA. Even with those
Cost Contour Plots of Biobased Commodity Chemical dierences, the MSP of isobutanol and 3-HPA are found to be
Production. The MSP of adipic acid, succinic acid, 1,3- nearly the same for a given titer, yield, and volumetric
propanediol, 3-HPA, and isobutanol are calculated for various productivity. For the detailed description of PFD of isobutanol
combinations of volumetric productivity, titer, and yield. The and 3-HPA production processes, please refer to the
cost contour plots that represent the relationship between Supporting Information.
MSP, yield, titer, and volumetric productivity are created for General Cost Contour Plots of Biobased Commodity
biobased commodity chemical production processes (Figures Chemical Production. Since the MSP of a biobased
S5S7). The comparison of cost contour plots shows that commodity chemical varies with the titer, yield, volumetric
biobased commodity chemical MSP is more sensitive to yield productivity, and the nature of cultivation, we generated general
than titer and productivity. For example, there is a nearly cost contour plots in terms of yield, titer, and volumetric
1000% increase in the biobased commodity chemical MSP, productivity for the aerobic and anaerobic/microaerobic
when the yield is decreased from 1 to 0.1 g/g for a certain titer production of biobased commodity chemicals (Figure 1). The
C DOI: 10.1021/acssuschemeng.7b01729
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

Figure 1. General cost contour plots for anaerobic production of a biobased commodity chemical with a productivity of (a) 1, (b) 2, and (c) 3 g/Lh;
for aerobic production of a commodity chemical with a productivity of (d) 1, (e) 2, and (f) 3 g/Lh. The cost contour lines represent MSP ($/kg) of
biocommodity chemicals.

data of MSP of 3-HPA is used to generate cost contour plots productivity to 3 from 2 g/Lh causes only a slight decrease in
for the anaerobic/microaerobic process, and the data of MSP of the MSP of a biobased commodity chemical (Figure 1). For a
1,3-propanediol that is produced via aerobic cultivation is used given titer and yield, the biobased commodity chemical MSP is
to generate general cost contour plots for the aerobic process. reduced approximately 3.5% when the productivity is improved
Comparison of general cost contour plots of anaerobic/ to 3 from 2 g/Lh (Figure 1). A similar comparison for the
microaerobic processes indicates that improving volumetric aerobic based commodity chemical production demonstrates a
D DOI: 10.1021/acssuschemeng.7b01729
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

Figure 2. General energy and GHG contour plots. (a) Energy plot for the anaerobic/microaerobic production of biobased commodity chemical (b)
and for aerobic production of biobased commodity chemical; (c) GHG plot for the anaerobic/microaerobic production of biobased commodity
chemical (d) and for aerobic production of biobased commodity chemical; energy contour lines represent total energy consumption (MJ/kg) of
biocommodity chemical production; GHG contour lines represent total GHG emissions (g CO2 equiv/kg) of biocommodity chemical production.

16% decrease in MSP (Figure 1). This is mainly due to there investments to develop a biocatalyst that synthesize glucaric
being no economy of scale advantage for aerobic processes. acid from glucose will not be protable.
A nonlinear relationship is found between the biocommodity Performance cost targets can be set to the biocatalyst
chemical MSP and the product titers. The economic benets of development team using the general contour plots of cost. For
improving fermentation titer beyond 125 g/L are found to be example, the average market price of adipic acid is 1.80
low for both aerobic and anaerobic/microaerobic biobased ($/kg.).27 For this target price, general cost contour plots in
commodity chemical production processes. For a certain Figure 1 shows various economically viable combinations of
productivity and yield, increasing titer to 200 from 125 g/L productivity, yield, and titer for making the adipic acid from
causes the biocommodity chemical MSP to drop only by 2% glucose using a biocatalyst. The yield, titer, and volumetric
(Figure 1). Thus, investments for pushing titers beyond 125 g/ productivity targets for the technology development team can
L must be avoided. be determined by selecting one viable combination. This
Use of General Cost Contour Plots of Biobased
selection can be done by comparing development time and
Commodity Chemical Production. The economic viability
costs that are required to develop a biocatalyst that exhibits
of new processes for the production of biobased commodity
chemicals using biocatalysts can be determined by utilizing each viable combination of process parameters. Such develop-
general cost contour plots. For example, glucaric acid can be ment time and costs can be qualitatively computed by the
made from sugar using E. coli under anaerobic conditions.28 management and research teams.
The theoretical yield and production rates of glucaric acid General Energy and GHG Contour Plots of Biobased
production are estimated at 0.3 g/g and 2 g/Lh, respectively, Commodity Chemical Production. The data of estimated
from stoichiometric calculations.29 The current market price of energy consumption and GHG emissions of biobased
glucaric acid is 0.80 ($/kg).27 For this market price, cost commodity chemical production processes are used to create
contour plots in Figure 1 shows that yields of greater than 0.8 contour plots of energy and GHG, respectively (Figures S8 and
g/g are necessary to make a process for the production of S9). The energy, GHG, and cost contour plots of biobased
glucaric acid that is economically viable. Since the required commodity chemical production processes have resulted in a
glucaric acid yield is greater than the theoretical yield, similar shape (Figures S5, S8, and S9). This indicates that there
E DOI: 10.1021/acssuschemeng.7b01729
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

Figure 3. Feasible space of processes for the production of (a) 3-HPA (anaerobic), (b) 1,3-propanediol (anaerobic), (c) adipic acid, (d) succinic
acid, (e) isobutanol, and (f) 3-HPA (microaerobic). The green curve represents the feasible cost curve, the red curve represents the feasible energy
curve, and the blue curve represents the feasible GHG curve. The purple vertical straight line indicates theoretical yields of biocommodity chemical
production.

is a correlation between economic and environmental perform- market prices are obtained from the ICIS chemicals pricing
ance metrics for the cases studied here. report.27 The cradle-to-gate energy consumption (MJ/kg) of
The comparison of GHG and energy contour plots indicates conventional adipic acid, succinic acid, isobutanol, 1,3-propane-
that the energy consumption and GHG emissions of biobased diol, and 3-HPA production processes are 124, 110, 60, 150,
commodity chemical production processes, except those made and 120, respectively.25,26 The cradle-to-gate GHG emissions
using aerobic cultivation, are found to be nearly the same for a (kg CO2 equiv/kg) of conventional adipic acid, succinic acid,
given combination of titer, yield, and productivity (Figures S8 isobutanol, 1,3-propanediol, and 3-HPA production processes
and S9). In addition, the decrease in the energy consumption are 9, 12, 3, 12, and 7, respectively.25,26 The feasible cost curves
and GHG emissions of anaerobic/microaerobic processes are are determined using both the market prices of chemicals and
found to be very low (0) when the volumetric productivity is general cost contour plots. For example, the market price of
increased from 1 to 2 g/Lh. The decrease in the energy adipic acid is 1.80 ($/kg.).27 The contour line of 1.80 in Figure
consumption (MJ/kg) and GHG emissions (kg CO2 equiv/kg) 1b represents the feasible MSP curve for adipic acid production.
of the aerobic process is around 2% and 0.2%, respectively, Similarly, feasible energy and GHG curves are determined using
when the productivity is increased from 1 to 2 g/Lh for a given general energy and GHG contour plots as well as cradle-to-gate
titer and yield (data is not shown). Like the biobased energy consumption and GHG emissions of conventional
commodity chemical MSP, the general counter plots of GHG processes, respectively.
and energy are generated for the processes of biobased The 2D-feasible space of biobased adipic acid, succinic acid,
commodity chemical production (Figure 2). Like the MSP isobutanol, 1,3-propanediol, and 3-HPA production processes
contour plots, the general GHG and energy contour plots are dened by graphing feasible cost, energy, and GHG curves
shown in Figure 2 can be used to screen early stage biobased along with yield, titer, and productivity constraints (Figure 3).
commodity chemical processes in terms of environmental The theoretical yields of biobased commodity chemicals are
performance and to set environmental performance targets for used to determine the yield constraints (Table 1). Titer of 200
new biocatalytic technology developments by governmental g/L and productivity of 2 g/Lh are assumed as titer and
policy makers. volumetric productivity constraints, respectively. We have
2D-Feasible Spaces of Biobased Commodity Chem- provided justication for the selected limits on titer and
ical Production. Conventionally, adipic acid, succinic acid, productivity in the supplement materials. The bounded space
isobutanol, 1,3-propanediol, and 3-HPA can be produced from between feasible energy or GHG curve and constraints of yield
a petroleum feedstock.25,26 The market prices ($/kg) of adipic and titer is dened as the environmental feasible space (Figure
acid, succinic acid, isobutanol solvent, 1,3-propanediol, and 3- 3). Similarly, feasible cost space is dened as a space between
HPA are 1.80, 1.80, 2.2, 1.70, and 1.60 respectively. These the feasible cost curve and constraints of yield and titer (Figure
F DOI: 10.1021/acssuschemeng.7b01729
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

3). For the selected constraint values, the feasible space is not Detailed PFDs, modeling assumptions, microbial pro-
found for the production of 1,3-propanediol via aerobic duction pathways, operating cost assumptions, micro-
cultivation. This is because the requirement of high capital aerobic reactor cost, DDGS price sensitivity, and
and operating costs for the aerobic cultivation process. additional information about results (PDF)


The comparison of feasible spaces of processes for the
production of biobased commodity chemicals shows that a AUTHOR INFORMATION
biocatalyst must exhibit titers of at least 45 g/L (Figure 3). If Corresponding Author
the toxicity of a biobased commodity chemical to biocatalyst *E-mail: anex@wisc.edu.
limits the concentration of a chemical in the fermentation
systems to lower than 45 g/L, the additional investments to ORCID
increase the yield and product rates of the biocatalyst will Sampath Gunukula: 0000-0001-7297-3993
become unviable (Figure 3). In such cases, the investments Notes
should be diverted to develop an alternate biocatalyst to make The authors declare no competing nancial interest.
the biobased commodity chemical. Similarly, a biocatalyst
development team must achieve biobased commodity chemical
yields of at least 0.32 g/g (Figure 3). To avoid potential losses,
ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
R&D investments to develop biocatalysts should be avoided [grant no. EEC-0813570/1158833].
when theoretical yields of biobased commodity chemicals are
less than 0.32 g/g. These values of yield and titer can be used as
general guidelines in the development of biocatalytic
REFERENCES
(1) Top Value Added Chemicals from Biomass. Vol. I-Results of
technologies. Screening for Potential Candidates from Sugars and Synthesis Gas.
The comparison of feasible spaces of processes for the NREL/TP-510-35523; National Renewable Energy Lab: Golden, CO,
production of biobased commodity chemicals shows that the 2004; http://www.nrel.gov/docs/fy04osti/35523.pdf (accessed 05/
feasible cost curve is always above the feasible GHG and energy 30/2017).
(2) Kharaka, Y. K.; Dorsey, N. S. Environmental issues of petroleum
curves (Figure 3). What that means is feasible environmental exploration and production: Introduction. Environ. Geosci. 2005, 12
space is always larger than the feasible cost space. This nding (2), 61.
indicates that if a biocommodity chemical production process is (3) Brehmer, B.; Boom, R. M.; Sanders, J. Maximum fossil fuel
found to be economically feasible, then the environmental feedstock replacement potential of petrochemicals via biorefineries.
performance of the biobased commodity chemical route will be Chem. Eng. Res. Des. 2009, 87 (9), 1103.
equal or better than that of conventional petrochemical route. (4) Gunukula, S.; Keeling, P. L.; Anex, R. Risk advantages of platform
Feedstock is the dominant cost in any commercially viable technologies for biorenewable chemical production. Chem. Eng. Res.
biobased commodity chemical production system. To test this Des. 2016, 107, 24.
(5) Lee, S. K.; Chou, H.; Ham, T. S.; Lee, T. S.; Keasling, J. D.
hypothesis, the MSP of biobased commodity chemicals Metabolic engineering of microorganisms for biofuels production:
estimated at the yield of 0.4 g/g (0.36 g/g for isobutanol), from bugs to synthetic biology to fuels. Curr. Opin. Biotechnol. 2008,
volumetric productivity of 2 g/Lh, and titer of 150 g/L is 19 (6), 556.
segmented into individual cost components. As shown in (6) From the sugar platform to biofuels and biochemicals. Contract
Figure 3, it is commercially viable to make a biocommodity No. ENER/C2/423-2012/S12.673791; European Commission: 2015;
chemical for these process parameter values. It has been found http://ibcarb.com/wp-content/uploads/EC-Sugar-Platform-nal-
from the comparison of individual cost components, that the report.pdf (accessed 05/30/2017).
(7) Gunukula, S.; Anex, R. Evaluating and guiding the development
feedstock cost dominates the MSP of a biobased commodity
of sustainable biorenewable chemicals with feasible space analysis.
chemical by >45% (data is not shown). Biochem. Eng. J. 2017, 119, 74.
In this study, we analyzed economic and environmental (8) Furlan, F. F.; Costa, C. B. B.; Secchi, A. R.; Woodley, J. M.;
potential of multiple biobased commodity chemical processes. Giordano, R. C. Retro-technoeconomic analysis: Using (bio)process
The general cost, energy, and GHG contour plots that are systems engineering tools to attain process target values. Ind. Eng.
determined in this study can be used to quickly assess Chem. Res. 2016, 55 (37), 9865.
economic and environmental viability of early stage biocatalyst (9) Tufvesson, P.; Lima-Ramos, J.; Nordblad, M.; Woodley, J. M.
based commodity chemical technologies. The use of these Guidelines and cost analysis for catalyst production in biocatalytic
processes. Org. Process Res. Dev. 2011, 15 (1), 266.
contour plots, therefore, avoids missing opportunities for
(10) Lynd, L. R.; Wang, M. Q. A product non-specific framework for
investments in the development of potential biocatalytic evaluating the potential of biomass-based products to displace fossil
technologies. In addition, process performance targets can be fuels. J. Ind. Ecol. 2003, 7 (34), 17.
set for use by technology development teams using these (11) Chotani, G.; Dodge, T.; Hsu, A.; Kumar, M.; LaDuca, R.;
general contour plots and the general rules found from this Trimbur, D.; Weyler, W.; Sanford, K. The commercial production of
study. Using these targets and guidelines, rms can be more chemicals using pathway engineering. Biochim. Biophys. Acta, Protein
eective in research and development of emerging biocatalytic Struct. Mol. Enzymol. 2000, 1543 (2), 434.
technologies to produce biobased commodity chemicals. (12) Cysewski, G. R.; Wilke, C. R. Process design and economic

studies of alternative fermentation methods for the production of


ethanol. Biotechnol. Bioeng. 1978, 20 (9), 1421.
ASSOCIATED CONTENT (13) Yuzbashev, T. V.; Yuzbasheva, E. Y.; Laptev, I. A.; Sobolevskaya,
*
S Supporting Information
T. I.; Vybornaya, T. V.; Larina, A. S.; Gvilava, I. T.; Antonova, S. V.;
Sineoky, S. P. Is it possible to produce succinic acid at a low pH?
The Supporting Information is available free of charge on the Bioeng. Bugs 2011, 2 (2), 115.
ACS Publications website at DOI: 10.1021/acssusche- (14) Large scale microbial production of advanced biofuels: How big
meng.7b01729. can we go? http://www.biofuelsdigest.com/bdigest/2014/12/07/

G DOI: 10.1021/acssuschemeng.7b01729
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX
ACS Sustainable Chemistry & Engineering Research Article

large-scale-microbial-production-of-advanced-biofuels-how-big-can-we-
go/ (accessed 05/30/2017).
(15) Harrison, R. G.; Todd, P. W.; Rudge, S. R.; Petrides, D. P.
Bioseparations Science and Engineering; Oxford University Press: New
York, 2003.
(16) El-Mansi, E. M. T.; Bryce, C. F. A.; Demain, A. L.; Allman, A. R.
Fermentation Microbiology and Biotechnology; Wiley: New York, 2004.
(17) Tao, L.; Tan, E. C. D.; McCormick, R.; Zhang, M.; Aden, A.;
He, X.; Zigler, B. T. Techno-economic analysis and life-cycle
assessment of cellulosic isobutanol and comparison with cellulosic
ethanol and n-butanol. Biofuels, Bioprod. Biorefin. 2014, 8 (1), 30.
(18) Gnansounou, E.; Dauriat, A. Technoeconomic analysis of
lignocellulosic ethanol: A review. Bioresour. Technol. 2010, 101 (13),
4980.
(19) Belter, P.; Cussler, E.; Hu, W. Bioseparations: Downstream
processing for biotechnology; Wiley: New York, 1988.
(20) Kwiatkowski, J. R.; McAloon, A. J.; Taylor, F.; Johnston, D. B.
Modeling the process and costs of fuel ethanol production by the corn
dry-grind process. Ind. Crops Prod. 2006, 23 (3), 288.
(21) Seider, W. D.; Seader, J. D; Lewin, D. R.; Widagdo, S. Product
and Process Design Principles: Synthesis, Analysis, and Evaluation; Wiley
& Sons: Hoboken, NJ, 2010.
(22) Peters, M. S.; Timmerhaus, K. D. Plant Design and Economics for
Chemical Engineers; McGraw-Hill: New York, 1991.
(23) Weidema, B. P.; Bauer, C.; Hischier, R.; Mutel, C.; Nemecek,
T.; Reinhard, J.; Vadenbo, O. C.; Wernet, G. The ecoinvent database:
Overview and methodology. Data quality guideline for the ecoinvent
database, version 3; 2013.
(24) Guinee, J. B. Handbook on life cycle assessment operational guide to
the ISO standards; Kluwer Academic Publishers: New York, 2002.
(25) Adom, F.; Dunn, J. B.; Han, J.; Sather, N. Life-cycle fossil energy
consumption and greenhouse gas emissions of bioderived chemicals
and their conventional counterparts. Environ. Sci. Technol. 2014, 48
(24), 14624.
(26) Cok, B.; Tsiropoulos, I.; Roes, A. L.; Patel, M. K. Succinic acid
production derived from carbohydrates: An energy and greenhouse
gas assessment of a platform chemical toward a bio-based economy.
Biofuels, Bioprod. Biorefin. 2014, 8 (1), 16.
(27) ICIS Chemical Pricing. http://www.icis.com/about/price-
reports/ (accessed 01/24/2017).
(28) Fruchey, O. S.; Manzer, L. E.; Dunuwila, D.; Keen, B. T.; Albin,
B. A.; Clinton, N. A.; Dombek, B. D. Processes for producing adipic
acid from fermentation broths containing diammonium adipate. US
Patent No. 2011/0269993A1, 2011.
(29) Cintolesi, A.; Clomburg, J. M.; Gonzalez, R. In silico assessment
of the metabolic capabilities of an engineered functional reversal of the
-oxidation cycle for the synthesis of longer-chain (C 4) products.
Metab. Eng. 2014, 23, 100.
(30) Burgard, A. P.; Van Dien, S. J. Methods and organisms for
growth-coupled production of 3-hydroxypropionic acid. US Patent
8673601B2, 2014.
(31) Lynch, M. D.; Gill, R. T.; Lipscomb, T. E. W. Methods for
producing 3-hydroxypropionic acid and other products. US Patent
9388419B2, 2016.
(32) Rush, B. J.; Fosmer, A. M. Methods for succinate production.
US Patent 2014/0363862 A1, 2014.
(33) Bastian, S.; Liu, X.; Meyerowitz, J. T.; Snow, C. D.; Chen, M.
M.; Arnold, F. H. Engineered ketol-acid reductoisomerase and alcohol
dehydrogenase enable anaerobic 2-methylpropan-1-ol production at
theoretical yield in Escherichia coli. Metab. Eng. 2011, 13 (3), 345.
(34) Rao, Z.; Ma, Z.; Shen, W.; Fang, H.; Zhuge, J.; Wang, X.
Engineered Saccharomyces cerevisiae that produces 1,3-propanediol
from D-glucose. J. Appl. Microbiol. 2008, 105 (6), 1768.
(35) Nakamura, C. E.; Whited, G. M. Metabolic engineering for the
microbial production of 1,3-propanediol. Curr. Opin. Biotechnol. 2003,
14 (5), 454.

H DOI: 10.1021/acssuschemeng.7b01729
ACS Sustainable Chem. Eng. XXXX, XXX, XXXXXX

You might also like