F11 Technologies for biofuels production

Building a "bio-perspective" from

petroleum revenues: a pathway through
Bioplatforms' Oriented Biofineries in Rio
de Janeiro State, Brazil
Victoria Santos, Energy Planning Program/COPPE/UFRJ, Brazil,
victoria_ens@ppe.ufrj.br

Alexandre Szklo, Energy Planning Program, Graduate School of Engineering,

Universidade Federal do Rio de Janeiro, Brazil, szklo@ppe.ufrj.br

Alessandra Magrini, Energy Planning Program, Graduate School of Engineering,

Universidade Federal do Rio de Janeiro, Brazil, ale@ppe.ufrj.br

Abstract
The city of Campos dos Goytacazes located on the north of the state of Rio de Janeiro,
Brazil ,is the main beneficiary from the countrys petroleum government take in
Brazil, perceiving more than 80% of the amount destined to cities. Until 2010, Campos
also held the second largest area for sugarcane crops in Brazil. However, Campos sugar
cane industry has been facing a strong retreat since the 1970s, due to the lack of
investment on research and new technologies coupled with a weak interorganizational
cooperation. On the other hand, the strong reliance of Campos on the O&G revenues
results in an economy based on a finite resource; a low level of economic diversity; and
the atrophy of a historically sound economic sector.

Hence, this study evaluates the potential for the development of sugarcane bagasse-
based biorefineries for the production of high valued bioplatform Molecules (bPMs).
Different schemes of distilleries were simulated aiming at estimating the potential
production of Levulinic and Succinic Acids, which are valuable inputs to
pharmaceuticals, cosmetics and solvents synthesis. The distilleries schemes vary from
replacing the expansion valve by a turbo expander to a highly modern industrial facility
including: turboexpander, high-pressure boilers (100 bar), and electromechanical
devices. The selected platforms derives from the acid hydrolysis of the sugarcane
bagasse followed by the fermentation of the hydrolysate. Results showed that the
production of high valued bPMs from sugarcane bagasse can contribute to the
competitiveness of sugarcane industry. Likewise, considering its multiplying effect, the
facility can also act as a driving force for the economy of the region.

Keywords

Brazil, sugarcane bagasse, biorefinery, bioplatform molecules, organic acids

Introduction
In response to a sum of factors including the hardening of environmental restrictions,
advances on biotechnology, companies drive for innovation and rising prices of oil and
its derivatives the world is watching the strengthening of the biorefinery concept as a
driver of an emerging bioindustry [1] [2].

Biorefineries can be defined as facilities where the biomass is used as feedstock to the
production of a range of products that goes from power and drop-in1 biofuels to
polymers and fine chemicals [3].

Currently the main challenges for the consolidation of biorefineries refer to the
availability of feedstock; lower cost pre-treatment, conversion, recovery and
purification technologies; product portfolio and market structure downstream.

Focusing on first and third issues, in terms of biomass, the use of cropland and edible
biomass for non-food purposes has been post under question once it threatens the
attractiveness of food production. As a result of that, residual biomass use is gaining
relevance into biorefining scenarios.

Sugarcane bagasse is an example of residual biomass. It is produced as leftover from

sugarcane processing for sugar and conventional ethanol production.

When it comes to the products portfolio, given the wide spectrum of possible products
from a biorefinery, some criteria can be used to help its setting. Under the value added
criterion, chemical products are said as providing the higher revenue per input biomass.

Bioplatform molecules (bPM) are an especially relevant category of chemical products

because of their broad market perspective. They consist of oxygenated chemical
intermediates having multiple functional groups that allow them to be converted into
new and valuable families of molecules. Usually, these molecules are also construction
blocks, which means they are also considered monomers, not changing their structure
to originate new products [3] [4].

Bio-Levulinic acid and bio-Succinic acid are two particular cases of bPM. Listed twice
as top value-added chemicals from biomass, these acids, among other chemicals, are
expected to lead the market of flourishing bioindustry. Currently, these organic acids are
obtained from petrochemical routes [4] [5].

This study hypothesis lays on the opportunity of revitalizing the sugarcane sector and
diversifying local economy from the use of surplus bagasse2 as feedstock of a bPM-
oriented biorefinery. The case analyzed refers to the Brazilian city Campos dos
Goytacazes, located in northern region of Rio de Janeiro State.

1
Drop-in products are defined as perfect substitutes to fossil products. Their use does not require further
adjustments on downstream or adaptation on equipment and transformation processes. They use existing
actives and expertise for fossil derivatives (Bomtempo, 2013).
2
Surplus bagasse is the amount of bagasse that remains after generating power to supply the respective
distillery demand.
Campos dos Goytacazes (or simply Campos), is the major city in Brazil in terms of
government take from petroleum production. It receives nearly 33% of total royalties
and special participation destined to cities, a total of nearly R$ 1.1 billion per annum.
This amount also represents 60% of its total income [6]. Therefore, Campos is a city
heavily relying on O&G revenues.

On the other hand, Campos was once known countrywide for a vigorous sugarcane
production. For instance, in 2010, it still held the second largest area for sugarcane
crops in Brazil [7]. The decline of Campos sugarcane sector started by the 1970s as the
result of a sum of factors, including the lack of investment on research and new
technologies coupled with a weak interorganizational cooperation and interruptions in
incentive programs from the government [8] [9].

Since the beginning of this movement downwards, there were some initiatives from
government and business sectors in order to strengthen Campos sugarcane production
again. Currently however its production yield just cannot go over half of Brazilians
average. Furthermore, Campos income from royalties which exist precisely to be
spent on initiatives that compensate for the extraction of a non-renewable resource is
almost completely used to supplement government expenditure [6].

Then, this paper evaluates the potential for the development of sugarcane bagasse-based
biorefineries oriented to the production of the bPMs Levulinic and Succinic acids based
on estimates of surplus bagasse availability at Campos dos Goytacazes city.

Under a local sustainable development bias, this research intends to provide

perspectives to the achievement of higher economic diversity and valorization of
renewable raw materials use. Also, it adds on to the idea of an O&G industry that can
act as an important driver to this purpose.

Methodology
This study was performed into three major steps. The first step aimed to identify
potential markets for Levulinic acid and Succinic acid. Then, different schemes of
distilleries3 were simulated aiming at evaluating the potential availability of surplus
bagasse. Finally, potential production of Levulinic and Succinic Acids was estimated.

Campos sugarcane sector situation allows for many investment options on existing and
new distilleries. Also, Brazilian actual park of distilleries presents a marked diversity of
process configurations. That is the reason why distinct process settings were taken into
account.

Another assumption of this study is that to enable the deployment of biorefineries, the
distillery processes efficiency should be improved in order to deliver the maximum
amount of surplus bagasse.

Potential markets for bio-Levulinic and bio-Succinic acids

3
In this study, sugarcane processing units producing ethanol and sugar.
A key step to propose a unit producing these bPMs in Brazil was to conduct a survey on
possible applications for these chemicals. As it comes to bPMs and building blocks
chemicals, their derivatives and fields of application are highly diverse.

Hence, scientific articles, specialized magazines, manufacturer catalogs, associations

reports and other documents were consulted in order to specify derivatives and their
respective manufacturers and production sites.

Sugarcane bagasse production

With the aim of covering a greater range of existing sugarcane processing facilities,
seven different schemes (or cases) of distilleries were proposed and analyzed. The
distinctions between them lie in the cogeneration process configurations, the low-
pressure steam demand and the motive powers driving forces. These aspects directly
influences the units efficiency and, therefore, the production of bagasse surpluses. The
base data for this step was taken from Dedini (2008), Horta Nogueira et. al. (2008),
Ramos et. al. (2008) and Ensinas et. al. (2009) [10] [11] [12] [13]. Table 1 presents the
main parameters of all the proposed cases.

Table 1 Distillery fixed parameters

Parameters Values

Sugarcane processing capacity (ton/hr) 500.0

Bagasse production capacity4 (ton/hr) 136.8

Operating days per year (d/yr) 180.0

Boiler thermal efficiency (%) 80.0

Bagasse (50% humidity) Low Heating Value (LHVbag) (Mcal/ton) 1,800.0

Produced Bagasse (50% humidity) per sugarcane processed(kg/ton) 273.6

The first scheme to be described represents almost 70% of Brazilian existing distilleries.
Therefore, it is also referred to as the reference configuration. It is characterized by a
relatively simple cogeneration process configuration, mainly compounded by a low-
pressure steam generator (boiler) followed by steam turbines for motive power, a single
stage backpressure turbogenerator and a reduction valve to provide low-pressure steam
to the sugar and alcohol production units.

The other conformations represent operational improvements on this one. Table 2

presents the operational conditions that characterize each scheme.

4
It was considered a production yield of 273.6 kg of bagasse per ton of sugarcane input.
Table 2 Operational conditions of configurations covered (1 represents reference
configuration above described).

Schemes
Operational Conditions
1 2 3 4 5 6 7
Boiler pressure
21.0 21.0 42.0 65.0 65.0 65.0 100.0
(kgf/cm)
Boiler temperature (C) 320.0 320.0 420.0 485.0 485.0 485.0 530.0
Low pressure steam
consumption per
500.0 500.0 500.0 500.0 400.0 400.0 300.0
sugarcane input (kg
/ton)
Distillery power
6.5 6.5 6.5 6.5 6.5 18.0 19.2
consumption (MW)
Distillery power
0.0 4.9 26.5 34.8 39.3 40.7 50.7
surplus (MW)

Recalling this studys assumption the surplus bagasse, instead of generating surplus
electricity for sale, would be destined to the production of bPMs.

The difference between the first and second configurations lays on the pressure
reduction system. In the latter, the reduction valve was replaced by a
condensation/extraction new turbogenerator (CD/EXT TG), which provides additional
electric power to the distillery.

In the third scheme, the low pressure boiler was replaced by a medium pressure one (42
kgf/cm and 420 C) and all steam generated was sent to the CD/EXT TG (steam at 21
kgf/cm was extracted from it and sent to steam turbines for motive power). In the
fourth case, the boiler is upgraded again to a 65 kgf/cm and 485 C one.

In the fifth scheme, the sugar and ethanol production processes were altered. The low-
pressure steam demand was reduced from 500 to 400 kg of steam per ton of sugarcane
input. This change results from attainment to maintenance schedule, operation at
product specification limit or proper thermal insulation of equipment and pipe.

Up to this point, all the proposed distillery cases have got the same electricity demand
(28,080 MWh/yr). However, this was changed in the sixth scheme. Instead of
equipment activated by steam turbines, the process now comprises electric machines.
Thus, the production of steam at 21 kgf/cm is no longer needed and the CD/EXT TG
yields more electricity to attend to the augmented demand.

Finally, the seventh configuration analyzed is characterized by another boiler upgrade

and another reduction of steam demand at sugar and ethanol production processes.

These schemes depict a typical operational improvement pathway for a sugarcane mill
in Brazil.
The amount of sugarcane bagasse in each of these cases was obtained from the material
and energy balances. For each case, the amount of surplus electricity obtained from
literature was converted back to bagasse. The result corresponds to the surplus bagasse
that could be available in each respective case.

An exception is made for the first configuration. Once it is the base case, it has not gone
through operational improvements. Also, there is no surplus power generation. Hence,
surplus bagasse available is the same from literature. The equations used for calculating
surplus bagasse estimates to the following cases are shown in Table 3.

Table 3 Equations used to compute surplus bagasse estimative for each covered
scheme.

No. Equations Descriptions

, , Fraction of power generated at TG

1 = 100 from steam expansion to each
, ,
pressure level
, ,
2 = TG energy balance
,

3 = , Boiler energy balance

,
Theoretical boiler bagasse input
4 =
flow
,
,

5 = Fixed boiler bagasse input flow
,
6 = + Surplus bagasse mass flow

Where the symbols are related to: i respective scheme (ranging from 1 to 7); j -
pressure level of the steam (21, 2.5 or 0.087 kgf/cm); e - from TGs upstream; s - from
TGs downstream; vap - steam related data; TG - TG related data; exc - surplus related
data; cald - boiler related data; t - unfixed data; bag - bagasse related data; r - fixed
data; p power percentage for each extraction or condensation pressure level (%); m -
mass flow (ton/hr); h - enthalpy (MJ/ton); W electrical power (MW); Q - heat load
(MJ/hr); C - heat capacity (MJ/ton/C); T - temperature difference (C); - boiler
thermal efficiency; and PCI - low heating value (MJ/ton).

To proceed the estimative for the second case, it was first obtained the boilers heat load
(Equation 3). Then, it was calculated the bagasse mass flow into the boiler without
taking into account its efficiency (Equation 4). After fixing this flow (Equation 6), total
surplus bagasse potentially available in the second configuration was found by summing
computed fixed bagasse flow with surplus bagasse of the previous configuration
(Equation 7).

From third to seventh cases, it was first estimated the steam mass flow used in power
generation before using procedure described above. This was accomplished by
computing the corresponding fraction from overall power produced by each extraction
point of the CD/EXT TG (Equation 1). Then, using this last data, the steam mass flow
was estimated (Equation 2). From this point on, the procedure followed the same of
second configuration. Table 4 presents the target variables in each equation used in this
methodology.

Table 4 Target variables from each equation used.

Schemes
No. Equations descriptions Target variables (unit)
1 2 3 4 5 6 7
Fraction of power
Fraction from overall
generated at TG from
1 power produced x x x x x
steam expansion to each
(dimensionless)
pressure level
2 TG energy balance Steam mass flow (ton/hr) x x x x x
Boilers heat load
3 Boiler energy balance x x x x x x
(kcal/hr)
Theoretical boilers
Theoretical boiler bagasse
4 bagasse mass flow x x x x x x
input flow
(ton/hr)
Fixed boiler bagasse input Fixed boilers bagasse
5 x x x x x x
flow mass flow (ton/hr)
Surplus bagasse mass
6 Surplus bagasse mass flow x x x x x x
flow (ton/hr)

Estimation of bPMs production

Once obtained the potential availability of surplus bagasse for the different distillery
configurations, it was evaluated the potential production of bio-Levulinic acid and bio-
Succinic acid. Base data on their production process were obtained from literature
[14][15].

Bio-Levulinic acid is considered to be produced under the Biofine Process. It consists of

two distinct acid-catalyzed stages. Initially, the lignocellulosic biomass5 is fractionated
into its free monomeric C5 and C6 sugars and other soluble intermediates through acid
hydrolysis. This transformation takes place in a plug-flow reactor. Then, this mixture
undergoes multiple acid-catalyzed reactions in a back-mix reactor to produce Levulinic
acid as the major product and Formic acid as a byproduct. Residual char produced is
sent to power generation to fulfill the process demand.

Bio-Succinic acid is obtained biochemically. The process consists of a pretreatment

stage using Ammonia Fiber Explosion (AFEX), followed by a centrifugation step to
separate lignin solids from the cellulose and xylose-rich aqueous effluent. Lignin is then
dried and sent to the heat and power cogeneration unit. The aqueous effluent is sent to
the saccharification and co-fermentation train. There, cellulose is hydrolyzed to glucose
and co-fermented with xylose to yield Succinic acid.

The production yields for both processes, in terms of dried feedstock, are presented in
Table 5.

5
Dry basis.
Table 5 - Production yield used for estimation of bPMs potential production (dry basis).

Products Yield (g/g)

Levulinic acid 0.228
Succinic acid 0.320

This bio-Succinic acid production process is also a mean for carbon sequestration once
it consumes CO2, which act as acidification inhibitor.

Using production yield data, it was possible to estimate the potential production for the
considered bPMs for each analyzed configuration (Equation 7). The main assumption in
this step was an invariant yield under different production scales.

= , (7)

Where: corresponds to the product (bio-Levulinic acid or bio-Succinic acid); is as

subscript for dry basis; and is the chemical yield per bagasse consumed (g/g).

In this particular study, byproducts were not taken into account.

Discussion and result analysis

Using the presented methodology, the amount of surplus bagasse in the considered
cases are presented in Table 6. It should be remembered that this result is in wet basis
(50% of humidity).

Table 6 Results for surplus bagasse estimates.

Schemes

1 2 3 4 5 6 7
Surplus bagasse
11.4 23.7 67.4 86.0 99.7 114.1 129.5
estimative (ton/hr)
Surplus bagasse
increment per
12.3 43.8 18.6 13.6 14.4 15.5
configuration
(ton/hr)
Pct. of increment per
107.6 184.9 27.6 15.9 14.4 13.6
configuration (%)
Pct. of total bagasse
8.7 18.2 51.7 66.0 76.5 87.5 99.4
produced6 (%)

It can be noticed a consistent increase from one configuration to another. The major
growth occurs from case 2 to case 3 with 43.8 ton/hr of bagasse saved and total sum

6
It was subtracted from this value an amount of 6.5 ton/hr of bagasse which should be destined to
equipment startup.
corresponding to nearly 50% of the amount produced. The increments in subsequent
cases are far less expressive. Hence, a moderate investment is enough to provide a
significant change in process efficiency. In sum, a great amount of bagasse surplus
could be available for higher added value purposes if distillery power demands could be
met using a smaller amount of bagasse or with its replacement by straw, lignin and/or
biogas.

Regarding the estimated potential production of bio-Levulinic acid and bio-Succinic

acid, result shows a higher potential for the latter (Table 7).

Table 7 bio-Levulinic and bio-Succinic acids annual production estimate.

Schemes

1 2 3 4 5 6 7
bio-Levulinic
acid (10 11.23 23.32 66.42 84.74 98.17 112.36 127.58
ton/yr)
bio-Succinic
acid (10 15.76 32.72 93.21 118.93 137.79 157.69 179.06
ton/yr)

Also, the bio-Succinic acid market has been more dynamic than the bio-Levulinic acids
one. According to the research on potential markets, the existing commercial plants
producing bio-Succinic acid offer a price ranging from US$ 2860 to US$ 3000 per ton
[16] [17] [18] [19]. This may be understood as an indicative of a relatively higher
maturity and decreasing costs trends for this particular product.

The mainly envisioned markets to the bio-Succinic acid for the next years are that of
Butanediol (BDO), Poly Butylene Succinate (PBS) and polyurethanes [19].
Furthermore, according to the survey on potential final products and applications, we
have come up with more than 30 derivatives from Succinic acid, while only 14 from
Levulinic acid.

Another potential derivative both from Succinic or Levulinic acids is the n-Metil-
Pyrrolidone, which is used as solvent for recovering of acetylenes and olefins and also
used in aromatics extraction from feedstock streams in the petrochemical industry [20]
[21]. This potential application may imply a perspective of an O&G industry leveraging
biorefineries deployment.

Both referred bPMs have got perspectives to become chemical commodities. For that
reason their prices are expected to be steadily reduced until 2020, especially when
destined to polymers production. At the same time, the market for fine and specialty
chemicals production must remain active [19].

Indeed, it is been said that a mix of high-value small-volume plus lower-value high-
volume products is the ideal portfolio for a profitable and economically sustained
biorefinery [3] [22] [23].
Regarding the city of Campos, the use of surplus bagasse into bPMs oriented
biorefineries presents a relevant potential to strengthen and diversify its local economy
and revitalize sugarcane-based activities. For instance, the upgrade of one of the local
distilleries to the 3rd case proposed in this study could provide Campos with more than
93 thousand tons of bio-Succinic acid per year. This is more than twice of current
installed capacity and may represent annual revenue of US$ 266 million.

Also, Campos holds a branch of Corbion Purac. It is one of the biggest companies when
it comes to lactic acid and its final products derivatives, from which Poly Lactic Acid
(PLA) is one example. In analyzed literature, there are perspectives that PBS will be an
alternative to PLA. PBS is one of bio-Succinic acids derivatives with great growth
perspectives and it is already being industrially produced.

Final remarks
This research is the first step of a broader analysis of opportunities and effects of
biorefineries implementation in Brazil. It analyses opportunities to build more
sustainable perspectives for the city of Campos dos Goytacazes RJ/Brazil.

After years of O&G revenues, it is not observed an associated improvement in its social
and environmental areas. Besides, some once relevant economic sectors kept a trend
downwards in their performance, which is especially true to Campos sugarcane sector,
a renewable source-based activity that is barely surviving nowadays.

Results showed that the production of high valued bPMs from sugarcane bagasse can
contribute to the competitiveness of sugarcane industry. Likewise, considering its
multiplying effect, the biorefinery can also act as a driving force for the economy of the
region. It also tries to envision an O&G industry collaborative with this revitalization
process once the facility may provide a supply alternative.

The next studies of this research group regards the analysis of economic, social and
environmental impacts of biorefineries in Brazil using Input-Output Analysis, and the
evaluation of possible value chains for the deployment of such facilities according to
social, economic and environmental criteria using Life Cycle Assessment and Industrial
Ecology tools.

This research was supported by the Foundation for Research Support of the State of Rio
de Janeiro (FAPERJ) and the National Agency of Petroleum, Natural Gas and Biofuels
(ANP).

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