Trabalho apresentado para obtenção do título de especialista em

Agronegócios – 2017

Biorefinery value-chain analysis: technology, commercialization and

sustainability

Anuj Kumar Chandel¹; Juliana Ramiro2

1 Department of Biotechnology, Engineering School of Lorena, University of São Paulo, Lorena (SP), Brazil
2PECEGE –Associate Researcher, Doctor in Science (Plant Pathology) – Rua Alexandre Herculano,120 –
Vila Monteiro – CEP13418-445 - Piracicaba (SP), Brazil

1
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Biorefinery value-chain analysis: technology, commercialization and

sustainability

Abstract

Biorefinery offers several promising opportunities to replace petroleum based

products and fuels in a sustainable manner paving to establish carbon neutral and
circular economy. Biorefinery has the potential to replace petroleum derived chemicals
(330 million tones) and energy. Currently bio-based chemicals and polymers production
is 50 million tones. The major bottleneck in biorefinery based operations is the economic
production of second-generation (2G) or cellulosic sugars which serve as building blocks
in renewable economy. This study deals with the survey on biochemicals and biofuels
production, technological status of various biochemicals and biofuels, pretreatment
technological scouting, biorefinery complexity profile and SWOT [Strength, Weakness,
Opportunities and Threats] analysis of biorefinery. Based on the simulation of 2G ethanol
production from major lignocellulosic biomass considering the steam explosion process
for pretreatment (85% hemicellulosic sugars recovery) and enzymatic hydrolysis (70%
cellulosic sugars recovery), Miscanthus and Sugarcane bagasse showed maximum total
2G sugars production of 581 and 540 Kg sugars/ton biomass respectively. Proximate
conversion of these sugars into ethanol (75% conversion yield), Miscanthus and
Sugarcane bagasse showed 222 and 207 Kg ethanol/ton sugars respectively. In addition
to 2G ethanol, high commercial value-based chemicals such as 1, 3 propanediol,
polylatic acid, polyhydroxy alkonoate, succinic acid, adipic acid, isoprene and other
potential biochemicals can be produced under biorefinery concept. In order to
biorefineries need to remain economically competitive, continuous innovation, increased
efficiency and regular development of new products and value streams addition are
necessary. For this, reliable supply chain for regular and sufficient feedstock supply at
stable price and partnerships is also necessary.
Key-words: Bio-chemicals; Technological survey; Bioethanol; Biobased industries

Introduction

Globally the largest fraction of energy, chemicals and materials, came from fossil
fuel refineries. However, the tendency of the availability of this non-renewable resource
is expected to be decreased in the coming years (Cherubini, 2010). Beside this, the large
emission of greenhouse gases produced from the combustion of fossil fuels or producing
chemicals is posing a negative impact on climate and ecosystems on the Earth (de Jong
and Jungmeier, 2015). These concerns have generated the needs to develop green and
sustainable processes for the conversion of renewable feedstock to bioenergy,
biochemical and biomaterials to meet the energy and commercial demand of society
(Silva and Chandel, 2014; Candel and Silveira, 2017).
Biorefinery refers to the “the sustainable processing of biomass into a spectrum
of marketable products and energy” (Cherubini, 2010). The term biorefinery
encompasses a network of facilities that integrate different technologies (processes and
equipment) to separate the constituents of biomass in their building blocks

2
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

(carbohydrates, proteins, triglycerides) that can be transformed into value added

products Such as biofuels, energy, materials and chemicals (Kamm and Kamm, 2004;
FitzPatrick et al., 2014; Sanford et al., 2016) (Figure 1 and Figure 2).

Gasoline
Ethanol
Refinery gas, plastic
Xylitol, organic acids
Grease and wax and
Butanediol, solvents
others
and others

Figure 1. General depiction of Petro-refinery and Bio-refinery and their major products
Source: Results from the present study

Figure 2. Configurational pathways for the production of various biochemicals from the
sugar platforms
Source: Elaborated by the author, adapted from Taylor et al. (2015)

This work presents the estimative analysis of bioethanol production from major
biomass sources, technological survey, biorefinery value chain analysis, biochemicals
production and the SWOT [Strength, Weakness, Opportunities and Threats] analysis of

3
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

biorefinery.

Methodology

Selection of Potential bio-products analysis and sustainability profile

Authentic literature survey and analysis was done thorough various reports
published by commercial agencies such as Competitiveness cluster-industries & agro-
resources-France, Nova institute-biobased economy-Germany (IAR, 2014; NOVA,
2015). Detailed scientific literature was analyzed for scientific and business discipline in
addition to personal communications with the peer researchers and other authentic
sources.
Survey on demand and market projections were assessed from bioeconomy
market reports from international energy agency (IEA, 2016). Personal communications
were also made with project managers working on sustainable bio-economy, industries
and academic institutes in Brazil and other countries to have the updates in the sector.

Biomass availability and chemical composition profile

Composition of potential biomass resources like sugarcane juice, corn grains (Ist
generation feedstock) and sugarcane biomass, corn biomass (IInd generation feedstock)
and others were assessed from Biomass compositional analysis, National renewable
energy laboratory (NREL, 2009) methods. Efforts were made to get the maximum
available information from authentic literature, peer reviewed publications and other
reliable source of information.
Feedstock composition (cellulose, hemicellulose, lignin-acid soluble and Klason
lignin, and ash) was determined using NREL standard Laboratory Analytical Procedures
[NREL-LAP] for the determination of the composition of biomass (Sluiter et al., 2008).
Potential biomass conversion yields (sugars from cellulose and hemicellulose
fraction of plant biomass) and the final product (ethanol and biochemical) were calculated
from the stoichiometric equations on molecular weight basis (Table 1).

4
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Table 1. Pretreatment Hydrolysis Reactions and Assumed Conversions by National

Renewable Energy Laboratory
Stoichiometric equations Component % conversion
(Glucan)n + n H2O→ n Glucose Glucan 9.9
(Glucan)n + n H2O → n Glucose Oligomers Glucan 0.3
(Glucan)n → n HMF + 2n H2O Glucan 0.3
Sucrose → HMF + Glucose + 2 H2O Sucrose 100
(Xylan)n + n H2O→ n Xylose Xylan 90.0
(Xylan)n + m H2O → m Xylose Oligomer Xylan 2.4
(Xylan)n → n Furfural + 2n H2O Xylan 5.0
Acetate → Acetic Acid Acetate 100
(Lignin)n → n Soluble Lignin Lignin 5.0
Source: Sluiter et al. (2009)

NREL energy calculator was also used to calculate potential bioconversion yields
along with technical publications available in scientific literature.
Glucan conversion (%) = (Glucose concentration (g L-1) X Volume)/ (Glucan
content in pretreated substrate X 1.11) * 100
Xylan conversion (%) = (Xylose concentration (g L-1) X Volume)/ (Xylan content
in pretreated substrate X 1.14) * 100
Ethanol conversion eq. (1), Conversion of cellulose to ethanol (%) = [EtOH] f ∗
biomass ∗ 1.111 ∗ 0.51 ∗ 100%.

Glucose 2 Ethanol + 2 CO2 (1)

3 Xylose 5 Ethanol + 5 CO2

where, [EtOH] is ethanol produced (g L-1); f is cellulose fraction of dry biomass (g g-1);
Biomass is dry biomass concentration at the zero hour of the fermentation (g L-1); 0.51
is conversion factor for glucose or xylose to ethanol based on stoichiometric biochemistry
of yeast; 1.111 is conversion factor of cellulose to equivalent glucose.

Technology scouting and business partnership model

Technology scouting was done to assess the profile of various pretreatment
technologies applied for lignocellulose biomass in industries for renewable sugars so
called second-generation [2G] sugars production (Alvira et al., 2010). These sugars are
considered as principle building block for renewable chemicals and biofuels production.
Various parameters like robustness of the process, capital expenses [CAPEX],
operational expenses [OPEX], process simplicity, minimum using of corrosive chemicals

5
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

and requirement of enzymes amount were the process variables while high sugars yield
with purity was the responsive variable. Sugars yield was the dependent variable as 2G
sugars are considered as the building blocks in biorefinery (IEA, 2016).

Biorefinery complexity profile [BCP] analysis

Biorefinery Complexity Index [BCI] was assessed for lignocellulose refinery (Jong
and Jungmeier, 2015). For each of the four features of a biorefinery the Technology
Readiness Level [TRL] was assessed using level range between 1 (“basic research”) to
9 (“system is ready for full commercial deployment”). Based on the TRL, the Feature
Complexity [FC] depends on each single feature of a biorefinery. With the number of
features and the FC of each single feature the Feature Complexity Index [FCI] for each
of the four features (platforms, feedstocks, products and processes) is analysed. The
BCI is the sum of the four FCIs. The Biorefinery Complexity Profile [BCP] is an integrated
format to present the complexity of a biorefinery by giving the BCI and the four FCIs of
each feature. The BCP, which includes the BCI and the four FCI has the following format:
BCP: BCI (FCIplatforms/FCIFeedstocks/FCIProducts/ FCIProcesses).
“BCP” of biorefinery is described by the Biorefinery Complexity Index is calculated
for the four features, as in eq. (2):

BCI = (NFPlattforms x FCPlatforms) + (NFFeedstocks x FCFeedstocks) + (NFProducts x FCProducts) + (2)

(NFProcesses x FCProcesses)

BCP = BCI (FCIPlatforms+FCIFeedstocks+FCIProducts+FCIProcesses)

Analysis on biorefinery commercialization and value creation

Based on the working experience and discussions with several professionals and
scientific literature, biorefinery commercialization status was analyzed (Bozell and
Peterson, 2010; Sanford et al., 2016). Additionally, the scale up issues were also critically
analyzed to set up bio-refinery at commercial scale (Sanford et al., 2016).

SWOT analysis

SWOT analysis of biorefinery was performed on the basis of scientific

deliverables and reports, expert knowledge, partner contributions and literature (IUS,

6
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

2014). Rather than doing SWOT analysis of each processes or platform in biorefinery for
single product, a complete biorefinery model was taken into consideration.
The general structure of a SWOT matrix is shown in Figure 3.

Success Failures

External Strengths Weakness

Internal Opportunities Threats

Figure 3. External and internal indicators used for SWOT analysis of Lignocellulose
biorefinery
Source: Results from the present study

Results and Discussion

Biorefinery and sustainability are complements to each other. In petroleum

refinery, physical, thermal and chemicals separation of crude oil are done into finished
products. On the other hand, biorefinery integrates the facilities for biomass conversion
into fuels, power, and chemicals. Biorefinery system is effective in mitigating climate
change, reducing dependency on imported gasoline and promoting cleaner production
chains relying on local and renewable feedstock (Cherubini and Jungmeier, 2010).
Sustainability is the base of any type of biorefinery. Biorefineries are still under
development and will have a decisive role in the global economy by 2030. As the
petroleum resources are depleting along with population increase, growing food/feed
demand, energy demand, biorefinery will have a catalytic role in supply the demand of
human requirement in sustainable manner (Erickson et al., 2012). Sustainable
development is defined in many ways but the most common definition is “development
that meets the needs of the present without compromising the ability of future
generations to meet their own needs” (Cherubini and Jungmeier, 2010). In the
sustainable development of biorefinery, People, Profit and Planet [3 P] are the three
major key stakeholders. People are linked with social, Profit is directly connected with
economic and Planet is interconnected with environment. Biorefinery in conjunction with
sustainability leads the green and prosperous world. Social development, economic

7
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

development and environmental sustainability lead to inclusive growth thus

strengthening the Circular economy or renewable economy as depicted in Figure 4.

Figure 4. Basic elements of biorefinery and relationship with sustainability indicators

Source: Results from the present study

Selection of Potential bio-products analysis and sustainability profile

In 2004, US Department of Energy (USDOE, Washington) has identified 12
platform bio-based chemicals which could be derived from sugars (first generation or
second generation) derived from sugarcane or corn and their residues or starch via
biochemical or chemical processes. These molecules can further have converted into a
large number of building block chemicals or materials with high added value.
➢ 1, 4 Succinic, fumaric and malic acids 2, 5 Furan dicarboxylic acid
➢ 3-Hydroxy propionic acid Aspartic acid
➢ Glutaric acid Glutamic acid
➢ Itaconic acid Levulinic acid
➢ 3-Hydroxybutyrolactone Glycerol
➢ Sorbitol

8
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Later in 2010, USDOE further revised the list of top 10 platform chemicals
based on green chemistry developments
➢ Ethanol
➢ Furans (furfural, 5-hydroxymethylfurfural, 2, 5-FDCA)
➢ Glycerol and its derivativos (propanediol, glycerol caronate, epichlorohydrin)
➢ Hydrocarbons (isoprenes…)
➢ Lactic acid
➢ Succinic acid/Aldehyde/3-hydroxy propionic acid
➢ Levulinic acid
➢ Sorbitol
➢ Xylitol
As per the DOE’s selection of 12 platform molecules and later the revised list,
some high value-added chemicals for example 2, 5 furan dicarboxylic acid [2, 5-FDCA],
3-hydroxypropionic acid, levulinic acid, succinic acid, and sorbitol are the common
platform chemical molecules.
Sugars directly obtained from plant (sugarcane, maize, beat root etc) or from
various biomass (sugarcane bagasse, corn stover, rice straw, wood etc) so called first
generation [1G] and second generation [2G] sugars are considered as primary building
blocks for biofuels and biochemicals production.
While the 1G sugars are easy to obtain from plants and is readily available, 2G
sugars are difficult to obtain as these come from plant cell wall carbohydrate polymers
i.e. cellulose and hemicellulose. Lignocellulosic materials are consisted of carbohydrate
polymers and lignin. Lignocellulosic biomass are the most abundant renewable organic
resources (~200 billion tons annually) on earth that are readily available for conversion
to ethanol and other value-added products (Chandel and Silveira, 2017). However, they
have not yet been harnessed for the commercial production of biofuel and renewable
chemicals. The lignocellulosic substrates include woody substrates such as hardwood
(birch and aspen, etc.) and softwood (spruce and pine, etc.), agro residues (wheat straw,
sugarcane bagasse, corn stover, etc.), dedicated energy crops (switch grass, and
Miscanthus etc.), weedy materials (Eicchornia crassipes, Lantana camara etc.), and
municipal solid waste (food and kitchen waste, etc.).

First generation [1G] biomass

Sugarcane juice, corn grains and sugar beet are three major feedstocks so called
1G biomass sources in the world which have potential in biorefineries to provide cheap

9
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

and clean sugars (1G sugars) as building block for ethanol and other biochemicals
production (Woiciechowski et al., 2016). Sugarcane is one of the most promising
alternative feedstock in countries like Brazil, India, China and some South American
countries. In Brazil, approximately 647.6 million tons sugarcane was produced in
2017/18 (Woiciechowski et al., 2016). In the current scenario in Brazil, ethanol, sugar
and electricity are produced from sugarcane. Sugarcane juice is directly used for sugar
production and fermented to ethanol. Almost sugars in free form or in cane juice and
fibers (bagasse and straw) are constituted in 1:1 ratio. Looking at the magnitude of
sugarcane production in Brazil, India and China, the sugars in cane juice has proven as
an excellent source of sugars, renewable ethanol and bio-chemicals production.
Corn is principle crop in world for fuels, food/feed renewable chemicals
production in the world. Particularly, in USA, nearly 351.3 million tons of corn was
produced in the 2013/2014. From 1 dry ton of corn 115 gallons of ethanol can be made.
Figure 5 categorically presents the 1G biomass composition.

Figure 5. Three main carbohydrate yielding crops in world and their composition
Source: Elaborated by the author, adapted and modified from Woiciechowski et al.
(2016)

10
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Second generation [2G] biomass

Usually, the remained lignocellulosic biomass (agro-residues, forestry waste,
energy crops and others) are used either for feed, fertilizer or household applications. A
significant portion of lignocellulosic biomass is openly burned in sugar mill’s boilers to
produce heat and power so called cogeneration [CHP] or left unused. Sugarcane
residues (bagasse or straw), corn stover, rice straw, energy crops and others are
promising source of complex carbohydrates which can be converted into ethanol and
biochemicals following the biorefinery concept. Around 200 billion tons lignocellulosic
biomass is produced annually. Lignocellulosic biomass is the cornerstone of biorefinery.
Table 2 shows the main lignocellulosic biomass sources, their carbohydrate amount,
lignin and practical 2G sugars yield from both the carbohydrate fraction.

Table 2. Second-generation sugars production profile from major various lignocellulosic

biomass available in the world
Biomass Carbohydrate Lignin 2G sugars conversion Total 2G
Cellulose Hemicellulose Cellulose Hemicellulose Glucose
conversion conversion +
into into xylose xylose)
glucose (85%) sugars
(70%)
--------------------%-----------------------
----------(Kg ton biomass-1)----------- ------------Kg ton biomass-1--------------
Sugarcane 42.3 28.8 24.7 296.1 244.8 540.9
bagasse (423) (288) (247)
Sugarcane 39.8 28.6 22.5 278.6 243.1 521.7
straw (398) (286) (225)
Corn 37.5 28.0 16.0 262.5 238 500.5
stover (375) (280) (160)
Rice straw 36.6 16.1 14.9 256.2 136.85 393
(366) (161) (149)
Wheat 39.7 26.2 18.1 278 222.7 500.7
straw (397) (262) (181)
Sorghum 35.9 26.0 7.52 251.09 221.34 472.38
straw (359) (260) (752)
Switch 34.8 31.5 23.5 243.6 267.75 511.35
grass (348) (315) (235)
Miscanthus 37.7 37.3 26.3 263.9 317.05 580.95
(377) (373) (263)
Arundo 36.3 30.0 28.5 254 255 509
donax (363) (300) (285)
Spruce 40.9 19.2 27.7 286.3 157.44 443.74
(409) (192) (277)
Birch wood 40.3 21.0 20.3 282.1 178.5 460.6
(403) (210) (203)
Source: Results from the present study

11
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Biomass processing includes steam explosion pretreatment, enzymatic

hydrolysis by commercial cellulase cocktail (Novozyme Cellic C Tec-2). During the
pretreatment by Steam explosion, 85% hemicellulose conversion and 70% cellulose
conversion during enzyme hydrolysis under industrial hydrolysis conditions (20% total
solids, 40 mg/g enzyme loading, 72 h hydrolysis). Table 3 presents the potential ethanol
conversion yield from the sugars recovered from each lignocellulosic biomass resources.

Table 3: Ethanol production from 2G sugars under separate hydrolysis and fermentation
(SHF) process. Theoretical ethanol yield is 511 g of ethanol produced/Kg of sugars while
practical ethanol yield in commercial 2G ethanol is only 75%

Theoretical Practical Ethanol

Biomass Cellulosic sugars
Ethanol yield yield*
kg ton biomass-1 kg ton sugars-1 kg ton sugars-1
1
Sugarcane bagasse 540.9 275.85 206.9
2
Sugarcane straw 521.7 266.06 199.55
3
Corn stover 500.5 255.25 191.44
4
Rice straw 393 200.43 150.32
5
Wheat straw 500.7 255.35 191.51
6
Sorghum straw 472.38 240.91 180.7
7
Switch grass 511.35 260.78 195.6
8
Miscanthus 580.95 296.28 222.21
9
Arundo donax 509 259.59 194.7
10
Spruce 443.74 226.30 169.73
11
Birch wood 460.6 234.90 176.17
Source: Results from the present study

There are several promising technological developments have been made in

university and industrial research and development laboratories in order to develop an
environmental friendly and economically competitive technology for the clean 2G sugars
production followed by a fermentative step for the bioconversion of these sugars into
ethanol and other biochemical (Ragauskas et al., 2006). In the current scenario, steam
explosion process as a pretreatment method is the most preferred method by industries.
The pretreated slurry (liquefied hemicellulosic content into C5 sugars solution and
cellulignin as solid residue in the slurry) is then enzymatically hydrolysed using the
commercial enzyme cocktail provided by Novozyme Inc, Curitiba, Brazil using high total
solids contents (>15% Total Soilds) for 48-72 hours. The slurry is then fermented as such

12
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

or supplemented with sugarcane juice or molasses in order to increase high total sugars
for the fermenting microorganisms for ethanol or biochemical production. Figure 6
presents the generalized process configuration used for 2G ethanol production which
can be adopted for biochemicals production also following the biorefinery concept. Figure
7 shows the cellulose and hemicellulose conversion from each major lignocellulosic
biomass.

Lignin Pyrolysis Separation

Biomass Pretreatment Hydrolysis

Electricity Phenols
Combustion and heat

C5 + C6 Ethanol
Sugars fermentation Distillation

Ethanol

Figure 6. Biorefinery platform using biomass for ethanol, heat and electricity and phenolis
production
Source: Results from the present study

13
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Total 2G (glucose + xylose) sugars (Kg/ton biomass)

Hemicellulose conversion into xylose (85% yield, Kg/ton)
Cellulose conversion into glucose (70% yield, Kg/ton)
Birch wood
Spruce
Arundo donax
Miscanthus
Switch grass
Sorghum straw
Wheat straw
Rice straw
Corn stover
Sugarcane straw
Sugarcane bagasse

0 100 200 300 400 500 600 700

Figure 7. Sugars (hemicellulosic, cellulosic and total 2G sugars) production profile (%

yield and Kg sugars produced from one ton of biomass) by steam explosion pretreatment
(12 bar pressure and 15 minutes) followed by enzymatic hydrolysis
Source: Results from the present study

This configurational process is the most common and simplified showing the
process flow feasible to industries. To produce the cost competitive ethanol or
biochemical in industries, this is necessary to minimize the bioconversion steps in order
to consolidate the process, minimizing the process reactions and equipment to save the
operational costs. However, this process configuration is well suited if all the sugars (C5
and C6) are fermented together for making ethanol. However, depending the
requirements of sugars for the use in production of specific products, the pretreated
slurry can be filtered to separate the C5 (hemicellulosic sugars) and then the recovered
solid fraction (cellulignin) is then sent for enzyme hydrolysis. In this way, both C5 sugars
and C6 sugars can be fermented for the production of different bioproducts or even the
same product by mixing together. Figure 8 presents the ethanol conversion profile from
sugars liberated from each lignocellulosic biomass.

14
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

700 Cellulosic sugars (Kg/ton biomass)

Theoretical Ethanol yield (Kg/ ton sugars)
600 Practical Ethanol yield* (Kg/ ton sugars)
500
400
300
200
100
0

Figure 8. Cellulosic (2G) sugars and ethanol conversion profile (75% conversions of
sugars into ethanol) from major lignocellulosic biomass
Source: Results from the present study

Biorefinery Technologies Assessment

Scouting of pretreatment technologies

In lignocellulose biorefinery, pretreatment of biomass is the inevitable process to
enable the 2G sugars which are brics of circular economy building. In last two or three
decades, significant progress has been made toward robust pretreatment process which
could be deployable in industries (Silva and Chandel, 2014). In fact, there are number of
pretreatment technologies exist, however only few matches with the industrial norms.
Technology scouting enabled the best technology suited to particular biomass and the
conditions of production facility. Parameters such as minimum CAPEX and OPEX, less
complexity and minimum inhibitors production were taken consideration while scouting
the pretreatment processes. Figure 9 summarizes the pretreatment technology scouting
process.

15
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Identification Selection Assessment Dissemination

Inovation status

1 2 R&D Status
3
10 8 6 4 5 6
Pilot & Demo
5 7 level
9 7

Full commercial
Various pretreatment Assessment of level
Selected pretreatment
technologies: technologies: pretreatment
1-Dilute acid hydrolysis 5-Steam explosion technologies:
2-Hydrothermal 6-AFEX • Easy operation
3-Organosolv 7-Alkaline • Low OPEX and
4-Ionic Liquid CAPEX
5-Steam explosion • High Sugars recovery
6-AFEX • Minimum inhibitors
7-Alkaline
8. Super-critical CO2
9-Phosphorus
10-H2O2

Figure 9. Lignocellulosic biomass pretreatment technology scouting or filtration

Source: Results from the present study

In the current scenario, only three pretreatment options such as Steam explosion,
Ammonia based pretreatment and dilute acid hydrolysis seem the most promising ones
which can be deployed in industries. However, number of reputed research groups and
startups are continuing the development of industrially feasible, robust and sustainable
pretreatment process.

Biorefinery complexity profile analysis

Biorefinery is a multidisciplinary and complex process which has several
processing steps. The complexity of biorefinery can be measured with different features
involved into the process (IEA, 2014). The number of different features of a biorefinery
directly influences the complexity. More number of features leads to more complexity of
biorefinery. The status of technology and number of features are the principle elements
of Biorefinery complexity profile [BCP]. If the complexity is very low then technology is
closer to attempt at commercial scale. The complexity decreases the closer a technology
is to a commercial application. These features eventually are taken into consideration to
calculate “Technology Readiness Level” [TRL]. TRL is measured from 1 - 10 scale. If the
TRL is close to 9 or 10 that means that technology is ready for commercial level. TRL is

16
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

basic parameter or assumption to analyze the Biorefinery Complexity Index [BCI]. The
complexity of biorefinery is connected with the number of features and TRL of each
feature.
+BCI and BCP are the numeric indication for the comparison of different
biorefinery concept and their potential.
+ BCP includes number of features such as platforms, feedstocks, processes and
products, and overall “TRL”.
+The higher the BCI, higher the complexity profile of biorefinery. BCP of a
biorefinery gives an indication on the technological and economic risks.
The Table 4 compares the biorefinery complexity index and profile of oil
biorefinery and Lignocellulose biorefinery.

Table 4. Biorefinery complexity index and profile of two most important refineries (Oil
biorefinery and Lignocellulose biorefinery)
Biorefinery
Type of Feedstock Number of
Product ranges complexity
Biorefinery used features
profile
Oil biorefinery (1G Oil seed
Biodiesel, 1+1+3+3 8
biorefinery) crops Glycerin and Feed
Lignocellulose Wood chips
Bioethanol, 8 + 1 + 4 + 16 29
refinery electricity, heat
and lignin
Source: Elaborated by the author, modified from de Jong and Jungmeier (2015)

Technology readiness level

Technology scouting is a method of technology forecasting in industrial corporate
sector. TRL can be taken into consideration to analyze the real scenarios of technologies
of biochemical/biofuels production. The National Aeronautics and Space Administration
[NASA] firstly introduced TRL, to characterize the technologies on a scale score from 1
to 9, the higher scored technology being those that are able to be employed at a
commercial scale. Table 5 shows the TRL of some biochemicals that can be produced
from lignocellulose fractionation in biorefinery.

17
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Table 5. Technology Readiness Level [TRL] of some biochemicals made from biomass
Theoretical
Market Theoretical
Compound TRL Market size market
price market value
value
ktpa USD t-1 Million USD year-1
Acetic acid 8-9 1357 617 837.3 Jubilant Lifescience
Ltd., India,
Songyuan Ji’an
Biochemical, China
Lactic acid 8-9 472 1450 684.4 Chongqing Bofei
Biochemical
Products, China;
Corbion Ltd, USA,
Henan Jindan,
HiSun, Wuhan,
China
Levulinic 6-7 3 6500 19.5 Segetis Inc, MN,
acid USA; Zibo
Shuangyu
Chemicals Ltd,
China
Acrylic Acid 5 0.3 2688 0.8 ADM Company, IL,
USA; BASF Inc,
Germany
5-HMF 5 0.02 2655 0.1 AVA Biochem Ltd,
Germany
Source: Elaborated by the author, adapted and modified from Chandel and Silveira
(2017)

Value-chain analysis
A realistic value-chain analysis is essential to assess the accurate potential of
lignocellulose biorefinery. Biorefinery is a vast untapped area which has the potential
make environment better, energy security and creating new jobs/employment. Further,
to meet the “20C” goal, it is advisable not to use oil resources, gas reserves and coal
reserves substantially by 2050 (IEA Bioenergy, 2015-www.ieabioenergy.com). In the
integrated biorefinery scenario, effective utilization of feedstock fractions will lead to a
diversified value-stream outputs and thus contribute to improvements of financial
performance and mitigation of potential risks (Bozell and Peterson, 2010). Figure 10
shows the general view of value-chain model of lignocellulose biorefinery. Each process
in integrated biorefinery is interconnected to each other and eventually showing the vast
range of products as an outcome of biorefinery.

18
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Agricultural Biomass Biomass Biorefinery Bio-based

inputs production trading inputs products

o Steam
o Seeds • Sugarcane § Biomass
o Chemicals
o Crops • Corn recovery o 2G sugars
o Enzymes
o Cultivation • Energy crops § Logistic and o Bio-Chemicals
o Microorganis
o Fertilizers • Short transportatio o Biofuels
ms
o Water rotation n o Bioenergy
o Water
o Maintenance crops § Processing o Food/feeds
o Filtration
• Forestry § Storage o Materials and others
waste

Biomass power Biorefinery

Heat byproducts (Yeast
Hydrolysis &
cream, lignin, oils
Fermentation
etc)

Figure 10. Components of Lignocellulose bio-refinery value-chain

Source: Results from the present study

Each segment as shown in Figure 10 has enormous opportunity in creating

business and value-aggregation. Agriculture inputs such as seeds, water, fertilizers and
maintenance are the basic elements of biorefinery. Crop grains or crop residues
production production are the backbone of biorefinery value creation. Here, crop
harvesting, biomass collection and transport, storage offers nice platform for job creation.
Thereafter, biomass including main crop material (grains or juice) are transported
(biomass trading) into mills/processing units and processed to end products. These
products (so called 1G sugars) are the building blocks of biorefinery. The fibrous residues
are processed which yields sugars (2G sugars) and lignin. Valorization of carbohydrates
(1G + 2G) needs multi-disciplinary processing steps. To assesses these sugars,
biorefinery inputs comprises steam, chemicals and enzymes are required. These sugars
alone or with 1G sugars can be fermented for biofuels and biochemical production in
biorefinery (Fitzpatrick et al., 2010). These sugars can add value-chain as several
products including biofuels can be produced (Table 6).

19
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Table 6. Commercial scale production of some biochemicals at biorefinery (continue)

Process and
Product Major Producer
capacity
Tons year-1
Cargill recombinant Bioamber 1250 René-Lévesque Blvd.
yeast technology West Suite 4310
Succinic acid
using corn syrup Montréal, Québec, Canada
30.000
Avantium Zekeringstraat 29
and BASF created 1014 BV Amsterdam
the joint venture The Netherlands
2, 5 Furan
Synvina to set-up
dicarboxylic acid
50,000 t/a plant for
the production of
FDCA from fructose
3-HP production by OPX BIO is working with Cargill,
3-Hydroxy fermentation of Novozyme and BASF to develop
propionic acid starch, 30 ton/year final product acrylic acid using 3-HP

Sugar and starch Flexible solutions International

Production process Ltd#206-920 Hillside Avenue Victoria,
under B. C. V8T 1Z8
Aspartic acid
development,
production capacity
is not yet confirmed
Sugar and starch Rivertop Renewables
Production process 1121 E. Broadway St
under Missoula, MT 59802
Glucaric acid
development,
estimated capacity:
4500 tons/year
Sugar and starch Meihua Holding Co Ltd.
Production Economic and Technical
Glutamic acid capacity: 400,000 Development Area, Langfang City,
tons/year Hebei Province 065001, China

Sugar and starch Qingdao Kehai Biochemistry Co Ltd

Production 3316 Sansha Road, Huangdao District,
Itaconic acid
capacity: 20,000 China
tons/year
Lignocellulosic Biofine Inc, 300, Bear Hill Road,
biomass Production Waltham, MA
Levulinic acid
capacity: 5,200
tons/year

20
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Table 6. Commercial scale production of some biochemicals at biorefinery (conclusion)

Product Process and capacity Major Producer

Production process Not available

under development, no
3-Hydroxybutyrolactone information on
commercial production

Production of 1,3 DuPont and Tate & Lyle

Propanediol (63,500 Zhangjiagang Glory
Glycerol and its based tons/year by DuPont Biomaterial Co. Ltd JiangSu
products (1, 3- and Tate & Lyle) and Province China
propanediol, 3 HP) 20,000 tons/year by for 1, 3-propanediol production
Glory Biomaterial Co. Ltd Metabolix for 3 HP production

Sugar/starch Roquette Freres 1003 South

Production process 5th Street PO Box 6647
Sorbitol fully developed Keokuk, IA 52632-6647
(347500 tons/year) USA

Glucose fermentation Aemetis Inc. 20400 Stevens

at commercial scale Creek Boulevard, Suite 700
Amyris collaboration Cupertino, CA 95014
with Micehlin and United States,
Braschem is under www.aemetis.com
Isoprene
development Amyris Inc (5885 Hollis
Street, Ste. 100
Emeryville, CA 94608,
USA)

Anaerobic fermentation Nature Works, LLC Blair, NE,

of corn syrup into lactic USA
Lactic acid or polylactic acid followed by
acid chemical conversion of
lactic acid into polylactic
acid 140 000 tons/year
Lignocellulosic Shandong Futaste
biomass Pharmaceutical Co. Ltd,
Xylitol Fully developed Qingado, China
production process
50,000 tons/year
Source: Elaborated by the author, adapted and modified from IAR (2015); Sanford et
al. (2016)

Another component of biomass residues is lignin which is energy intensive and

has not fully commercialized so far (Ragauskas et al., 2009). Currently, lignin is directly
sent to boilers for heat and electricity generation, However, research has shown that it

21
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

can be used as adsorbent, paints, polymers and ultra-refinery of lignin can leads to
several high economic value products (Ragauskas et al., 2009).

Major companies and their investment on bio chemicals and 2G ethanol

At global scale, renewable biochemicals (excluding biofuels) volume is around 50
billion kilos per year which is continuously growing with the rate of 3-4% per year (de
Jong et al., 2012). USA recorded 126 billion dollar direct sales of biochemicals in 2013.
Table 5 presents he information on interesting biochemicals (selected by NREL-2009,
CO, USA) the manufacturing company and production capacity of biochemicals
(excluding biofuels). For cellulosic ethanol production, several industries in the world
have set up pilot, demonstration and production facility using sugarcane bagasse,
sugarcane straw or corn stover. Table 7 presents some important examples of
companies who are taking lead in cellulosic ethanol production.

Table 7. Second-generation (2G) ethanol production at commercial scale

Feedstock/Technology Production capacity Company

Sugarcane bagasse, steam

Raízen Energia, Costa Pinto
explosion based
40 million litres/year sugar cane mill in Piracicaba,
pretreatment and hydrolysis
São Paulo
(Iogen process), yeast
fermentation

Sugarcane straw/bagasse Gran Bio and Beta

pretreatment via the 64 510 (21.6 MM gal./year) Renewables Sao Miguel dos
ProesaTM process, Campos, Alagoas, Brazil
hydrolysis, fermentation
Corn stover, pretreatment,
Poet-DSM Advanced
hydrolysis and yeast
59 734 (20 MM gal./year) Biofuels Emmetsburg, IA,
fermentation
USA
Corn stover pretreatment,
hydrolysis and yeast 74 667 (25 MM gal./year) Abengoa
fermentation Hugoton, KS, USA

DuPont Industrial
Corn stover, pretreatment,
89 600 (30 MM gal./year) BioSciences Nevada, IA,
hydrolysis, bacterial
USA
fermentation
Sugarcane bagasse,
Centro de Tecnologia
continuous steam
3 million litre per year Canaviera (CTC)-
explosion, hydrolysis and
Piracicaba, Brazil
yeast fermentation
Source: Elaborated by the author, dapted and modified from IAR (2014); Sanford et al.
(2016)

22
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Beside ethanol (1G or 2G) and other value-added products listed in Table…,
several other promising bio-chemicals based on plant cell wall chemistry have emerged
in recent years by the continuous R&D efforts from academic and industrial sector.
Ethylene (Braschem Inc., Brazil), Isobutanol (Gevo Inc Colorado, USA), Farnesene
(Amyris Inc, Brazil), Epicholorohydrin (PTT, Map Ta Phut, Thailand), p-Xylene (Virent,
Madison, WI, USA), Acrylic acid (ADM and BASF, Germany), Adipic acid (5-HMF (AVA
Biochem, Germany) and others are strong place in bioeconomy. Some of these
chemicals are considered as base or platform chemicals, intermediate chemicals for
developing further various household chemical commodities.

Simulation of Lignocellulose bio-refinery model and partnerships in

product development
Biorefinery at large addresses the major bio-based chemicals, biofuels and
biomaterials using the biomass resources under integrated approach. The base of
Biorefinery is the biomass. Figure 11 shows the lignocellulose biorefinery processing
covering major steps. Depending the availability of particular biomass in particular region
or country, biorefinery can be simulated. For example, Brazil, India and China could rely
on sugarcane residues or rice agro-residues while USA and European countries can
thrive on corn residues and forestry waste respectively. Economic production of sugars
(particularly 2G sugars) is the backbone of lignocellulose biorefinery. Cellulosic sugars
so called 2G sugars act as building block for biofuels and biochemicals production in
integrated biorefineries. A recent analysis by Lux research on cost economic model for
2G ethanol production by six major players (Beta Renewables, Poet + DSM, Granbio,
Abengoa, Raizen, Dow-Dupont), using feedstocks-Aurndo donax, corn stover,
sugarcane bagasse/straw, corn stover, sugarcane bagasse and corn stover respectively
and three pretreatment technologies (dilute acid, steam explosion and alkaline),
feedstock cost can impact nearly 40% and potentially around 16% cost can be reduced
by improvements in pretreatment yield, enzyme hydrolysis ad fermentation efficiency
(Luxresearch report, 2016). 2G sugars cost (~100 US$/ton) would be ideal to achieve
minimum ethanol selling price [MESP] of <2 US$/gallon. Both the sugars i.e. C5 and C6
sugars are in high demand in chemical industries. Players like Braschem and Amyris are
continuously looking forward to get a regular supply of C5 sugars for the production of
butadience and farnesene. In the current scenario, two types of pretreatments (steam
explosion and alkali), enzyme hydrolysis (at high total solids loadings >20%, Novozyme
Cellic CTec 3, 20 g enzyme Kg-1 pretreated biomass) and then fermentation of 2G sugars

23
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

by recombinant Sacchamromyces cerevisiae are main activities in 2G biorefinery.

However, mechanization of the overall process particularly in pretreatment is still a big
challenge in biorefineries. Remained lignin quantity is being sent to boilers for co-
generation of heat and electricity (CHP) (Figure 6). Lignin should be valorized in
judiciously manner rather than just burning in boilers (Ragauskas et al., 2014).
Partnerships at every front and level is crucial for the successful deployment of
lignocellulose biorefineries near future. Partnerships in any form (joint collaboration, turn-
key, technology licensing or sub-licensing, supply chain, production, service and utilities,
marketing etc) is pivotal for the desired success of biorefineries.

Supply on Supply
demand Agreement
Commercial Financial
• Technology Licesing Agreement Cooperation
• Technology Sub-Licesing
• Process Designing
• Production Parternship Market
Feedstock

End user
Intermediate
producer Final producer Supplier Distributor PRODUCT

PRODUCT DEVELOPMENT MARKETING

• Raw material supply • Supply chain management
• Technological development • Financial management
• Research and development • End user service and
• Process Engineering satisfaction

Figure 11. Trends and developments in biofuels or biochemical production partnerships

(Feedstock  Bio-products)
Source: Results from the present study

The Figure 11 presents the linkage between feedstock suppliers, technologies

and producers (intermediate and final producers), suppliers & distributors and product
development. In lignocellulose bio-refinery, continuous feedstock supply in sustainable
manner is the basic requirement. In annexed mills for 1st generation (sugarcane mills and
corn processing mills), feedstock such as sugarcane bagasse/straw and corn stover can
be remarkable for the regular supply chain for the successful continuous biorefinery
operations. For the product development, synergy between supply chain of feedstock via
supply agreement and then processing of this feedstock for the product development is
utmost important (IAR report, 2014). In the production phase, joint ventures in products

24
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

development, or bringing new technology from the third party is really important. For the
product development, technology licensing from third party or even turn-key agreement
is directly linked with the smooth production of first 2G sugars followed by the use of
these for 2G biofuels or biochemicals production. Post-production partnerships bring
commercial agreement between producer to supplier or distributor and marketing
companies of the product for the eventually delivering to the end user. In this line,
marketing umbrella should cover the supply chain and financial managements for the
supply of the product to the ultimate end user with service satisfaction. In reality,
partnerships in biorefinery via agreements or acquisitions to bring new technologies for
biomass pretreatment or 2G sugars production with competitive price and then
biotechnology product development is inevitable for the success of the individual
biorefinery (Bhowmick et al., 2017).

SWOT Analysis
SWOT analysis of biorefinery assess four important parameters i.e. strengths
(S), weaknesses (W) [internal factors], opportunities (O) and threats (T) [external factors]
from a business and strategic point of view. The results of the SWOT analysis of
biorefinery is shown in Figure 12.

25
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Figure 12. A general view on SWOT matrix of biorefineries

Source: Results from the present study

Biorefinery has several internal strengths and weaknesses. Geopolitical factors

such as climate change, de-carbonizing the fossil economy and uncertainty in availability
of fossil sources have led the way to look out the search for potential alternatives while
higher capital and operational investments and lacking of technical process maturity are
serious concerns (Chandel et al., 2017). Biorefineries have offered several promising
opportunities in terms of reduction of greenhouse gasses (GHG) emissions and several
major research outcome and positive interest of key chemical players in investing the
biorefinery projects (IEA, 2014). However, recent failures of cellulosic production projects
have shown substantial threats.

26
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Conclusions

Recent encouraging developments in biorefineries offer numerous opportunities

for the development of sustainable biofuels, biochemical and biomaterials. However,
there are several challenges exist for their uninterrupted production at commercial scale.
Surplus availability and pricing of biomass feedstock, capital, competition, market eco-
system and policy framework etc are required to be measured very precisely. The
formative conglomeration of agricultural economics, process engineering, modern
biotechnology and policy analysis is essential for the overall success of biorefineries in
long haul. Under biorefinery platform, integrated production of biofuels and biochemicals
in annexed facilities offer a clear-value proposition. Establishment of new supply chains
for biomass feedstock, partnerships at every level (inputs: supply chain, technology and
processing) and marketing are essential to build a sustainable and worldwide bio-based
economy.

Acknowledgement

Anuj K. Chandel is thankful to Centro de Tecnologia Canaviera [CTC]-Piracicaba,

and USP-CAPES, Sao Paulo, Brazil for researcher and visiting professorship.

References

Alvira, P.; Tomás-Pejó, E.; Ballesteros, M.; Negro, M. J. 2010. Pretreatment

technologies for an efficient bioethanol production process based on enzymatic
hydrolysis: a review. Bioresource Technology 101: 4851–4861.

Bozell, J.J.; Petersen, G.R. 2010. Technology development for the production of bio-
based products from bio-refinery carbohydrates – the US Department of Energy’s “Top
10” revisited. Green Chemistry 12: 539–554.

Chandel, A.K.; Silveira, M.H.L. 2017. Sugarcane bio-refinery: Technologies,

commercialization, policy issues and paradigm shift. Elsevier Press, Sao Paulo, Brazil.

Cherubini, F.; Jungmeier, G.; Wellisch, M.; Willke, T.; Skiadas, I.; van Ree, R. et al.
2009. Toward a common classification approach for biorefinery systems. Biofuels
Bioproducts Biorefining 3: 534–546.

Competitiveness cluster-industries & agro-resources-France [IAR]. 2014. Available at:

<www.iar-pole.com> Accessed on: 12 Aug. 2017

27
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

Bhowmick, DG.; Sarmah, A.K.; Sen, R. 2017.Lignocellulosic biorefinery as a model for

sustainable development of biofuels and value-added products (in press). doi:
https://doi.org/ 10.1016/j.biortech.2017.09.163

Erickson, B., Nelson, J.E.; Winters, P. 2012. Perspective on opportunities in industrial

biotechnology in renewable chemicals. Biotechnology Journal 7: 176–185.
FitzPatrick, M., Champagne, P., Cunningham, M.F., Whitney, R.A. 2010. A biorefinery
processing perspective: treatment of lignocellulosic materials for the production of
value-added products. Bioresource Technology101: 8915-8922.

Institute for environmental studies. [IUS]. 2014. SWOT analysis. Heidelberg. Germany.
Available at: <www.scribd.com>. Accessed on: 10 Aug. 2017.

International Energy Reports. [IEA]. 2014. The biorefinery complexity index. Graz.
Austria. Available at: <www.iea-bioenergy.task42-biorefineries.com> Accessed on: 10
Oct. 2017.

International Energy Reports. [IEA]. 2016.Bioenergy reports. Wageningen. The

Netherland. Available at: <www.ieabioenergy.com> Accessed on: 03 Aug. 2017

Jong, DE.; Jungmeier. 2015. Biorefinery Concept in comparison to petrochemical

refineries. p.3-33. In: Industrial Biorefineries and White Biotechnology. Elsevier Press
DOI http://dx.doi.org/10.1016/B978-0-444-63453-5.00001-X

Kamm, B.; Kamm, M. 2004. Principles of biorefineries. Applied Microbiology

Biotechnology 64:137–145.

National renewable energy laboratory [NREL] 2009. Biomass compositional analysis.

Colorado, USA. 2009. Available at: <www.nrel.gov> Accessed on: 12 Sep. 2017

Nova institute-biobased economy, Germany. [NOVA]. 2015. Available at: <www.nova-

institut.de/bio> Accessed on: 10 out. 2017

Ragauskas, A.J., Beckham, G.T., Biddy, M.J., Chandra, R., Chen, F., Davis, M.F., et
al. 2014. Lignin valorization: improving lignin processing in the biorefinery. Science
344, 1246843.

Ragauskas, A.J.; Williams, C.K.; Davison, B.H.; Britovse, K.G.; Cairney, J.; Eckert,
C.A. et al. 2006. The path forward for biofuels and biomaterials. Science 311: 484–489.

Sanford, K., Chotani, G., Danielson, N., Zahn, J.Á. 2016. Scaling up of renewable
chemicals. Current Opinion in Biotechnology 38: 112-122.

Silva SS and Chandel AK. 2014. Biofuels in Brazil: Fundamental aspects, recent
developments, and future perspectives. Springer Verlag, Heidelberg, Germany.

Sluiter, A.; Hames, B.; Ruiz, R; Scarlata, C.; Sluiter, J.; Templeton, D. 2008.
Determination of structural carbohydrates and lignin in biomass. Laboratory analytical
procedure 1617, 1-16.

Taylor, R.; Nattrass, L.; Alberts, G.; Robson, P.; Chudziak, C.; Bauen, A.; Libelli, L.;
Lotti, G.; Prussi, M.; Nistri, R. 2015. From the sugar platform to biofuels and

28
Trabalho apresentado para obtenção do título de especialista em
Agronegócios – 2017

biochemicals: final report for the European Commission Directorate-General Energy.

E4tech/Re-CORD/Wageningen UR; The Netherland.

Woiciechowski, A.L.; Medeiros, A.B.P.; Rodrigues, C.; Vandenberghe, L.P.S.; Tanobe,

V.O.A.; Agnol, A.D.; Gazzoni, D.L.; Soccol, C.R. 2016. Feedstocks for Biofuels. p. 15-
26. In: C.R. Soccol et al. (eds.), Green Fuels Technology, Springer International
Publishing, Switzerland. DOI 10.1007/978-3-319-30205-8_2

29