Riga Technical University

Faculty of Power and Electrical Engineering

Institute of Energy Systems and Environment

Master Thesis

LIFE CYCLE ASSESSMENT OF VINASSE PRODUCTION

FROM SUGARCANE IN BRAZIL, FOR A NEW BIO
ETHYLENE PRODUCTION PATHWAY.

Author Fabian Andres Diaz Sanchez

Supervisor Jūlija Gušča, Dr. sc. ing.

RTU 2019
 Confirmation
Master Thesis is developed at
the Institute of Energy Systems and Environment (IESE)

Author: Fabian Andres Diaz Sanchez _________________

(signature, date)

Scientific supervisor:
Dr.sc.ing., Jūlija Gusca
_________________
(signature, date)

Quality control: Dr.sc.ing., Dace Lauka

_________________
(signature, date)

The thesis is suggested for defense at the IESE Master thesis examination commission:

Director of the EEF IESE:

Dr.habil.sc.ing., professor Dagnija Blumberga
________________
(signature, date)

Master thesis is defended at the IESE Master thesis examination commission session on
June___, 2019 and evaluated with mark ______________.

Secretary of the Master Thesis

defense commission
_________________
(signature, date)

2
 Declaration of authorship
I, the undersigning, hereby declare that the Master’s Thesis entitled LIFE CYCLE
ASSESSMENT OF VINASSE PRODUCTION FROM SUGARCANE IN BRAZIL, FOR A
NEW BIO ETHYLENE PRODUCTION PATHWAY is, to the best of my knowledge and
belief, original and the result of my own investigations, except as acknowledged, and has not
been submitted, either in part or whole, for a degree at this or any other University.
Formulations and ideas taken from other sources are cited as such. This work has not been
published.

Fabian Andres, Diaz Sanchez…………………………….

Date: 31.05.2019.

3
 Supervisor task
Objective: to understand the environmental effects of bio ethylene production
(bioethanol to bio ethylene) from vinnase by performing a Life Cycle Assessment evaluation
for the vinnase production in a cradle to gate approach.
Suggested plan of the work

1. Literature review
a. Ethylene vs bio ethylene production amounts worldwide, the leading countries.
b. Why does a switch from ethylene to bio ethylene is required?
c.
2. Technological process of Bioethanol to bio ethylene
a. Bioresources used
b. Technologies used
c. Final products
3. Life cycle assessment
a. Functional unit, boundaries, scenarios
b. Inventory (data collection)
c. Model in SimaPro
d. Sensitivity analysis
i. Sensitivity to the method
ii. Sensitivity to electricity consumption
4. Conclusions

4
ANNOTATIONS

The title of the Master Thesis is Life cycle assessment of Vinasse production from sugarcane
in Brazil, for a new Bio ethylene production pathway.

The author of the work is Fabian Andres Diaz Sanchez.

The objective of the work is to assess the environmental impact of the Vinasee production in
Brazil using sugarcane as main raw material.

During the first chapter, literature review regarding the worldwide production of ethylene, its
market and forecast for the next few years is presented. The main methods for ethylene
production are shown and reviewed, with a brief introduction to the proposed new technology
for obtaining bio ethylene from anaerobic co-digestion of vinasse.

In the second chapter, the detailed new bio ethylene production process proposed is explained
focusing in the production of bioethanol and vinasse in Brazil, also, most of data collected for
the life cycle inventory is presented during this chapter.

For the third chapter, the life cycle assessment methodology is presented, scope, objectives and
boundaries are defined to finalize with the structured life cycle inventory used for the simulation
of the bioethanol production from sugarcane.

Finally, in the fourth and last chapter, results from the simulation using simapro software tool
are displayed, explained and discussed. Sensitivity analysis is also performed, and results are
explained in detail to evaluate the most susceptible areas for the pretend scenario.

The thesis includes 91 pages, 39 figures, 19 tables and 79 references.

5
ANOTACIONES

El título del trabajo de Tesis es Análisis de ciclo de vida de la producción de vinaza de caña de
azúcar en Brasil, en una nueva alternativa de producción de bio etileno.

El autor de la tesis es Fabian Andres Diaz Sanchez.

El objetivo principal de la tesis es la evaluación del impacto ambiental de la producción de

vinaza in Brasil usando caña de azúcar como principal materia prima.

En el primer capítulo, se discute la información disponible en textos sobre la producción

mundial de etileno, el mercado actual y el pronóstico para los siguientes años. También se
mencionan los principales métodos de producción de etileno y se incluye una breve descripción
del nuevo proceso tecnológico para su producción a partir de la codigestion anaeróbica de
vinaza.

En el segundo capítulo, se explica detalladamente la metodología para el nuevo proceso de

producción de bioetilieno propuesto, concentrándose en la producción de bioetanol y vinaza en
Brasil. La mayor parte de los valores usados para el inventario en la evaluación del ciclo de
vida es presentada en este capítulo.

Ya en el tercer capítulo, la metodología para el análisis de ciclo de vida es presentada, el

alcance, objetivos y límites son definidos para finalmente presentar el inventario estructurado
usado para la simulación de la producción de bioetanol y vinaza de caña de azúcar.

En el cuarto y último capítulo, los resultados obtenidos de la simulación realizada usando el

software simapro son presentados, explicados y discutidos. Se realizó también un análisis de
sensibilidad y los resultados son evaluados en detalle para identificar que tan susceptible es el
modelo a los escenarios simulados.

Esta tesis incluye 91 páginas, 39 figuras, 19 tablas y 79 referencias.

6
ANOTĀCIJAS

Promocijas darba nosaukums ir Vināzes ražošana no Brazīlijā iegūtām cukurniedrèm, tās dzīves
cikla novērtējums jauna bioetilēna ražošanas virziena attīstībai.

Promocijas darba autors ir Fabian Andres Diaz Sanchez.

Promocijas darba galvenais mērķis ir novērtēt Brazīlijas vīnogulāju ražošanas ietekmi uz vidi,
kā galveno izejvielu izmantojot cukurniedru.

Pirmajā nodaļā ir aplūkota informācija, kas pieejama tekstos par etilēna globālo ražošanu,
pašreizējo tirgu un prognozēm nākamajiem gadiem. Tika pieminētas arī galvenās etilēna
ražošanas metodes un īss apraksts par jauno tehnoloģisko procesu, kas paredzēts tā ražošanai
no vīnogulāju anaerobās kodifikācijas.

Otrajā nodaļā ir sīki izskaidrota ierosinātās jaunās bioetilīna ražošanas metodes metodika,
koncentrējoties uz bioetanola un vinasse ražošanu Brazīlijā. Šajā nodaļā ir sniegta lielākā daļa
inventarizācijas vērtību dzīves cikla novērtējumā.

Jau trešajā nodaļā ir izklāstīta dzīves cikla analīzes metodika, definēta darbības joma, mērķi un
ierobežojumi, lai visbeidzot prezentētu strukturēto uzskaiti, kas izmantota bioetanola un
cukurniedru vīna ražošanai.

Ceturtajā un pēdējā nodaļā tiek prezentēti, izskaidroti un apspriesti rezultāti, kas iegūti,
izmantojot simulācijas programmatūru, izmantojot simapro programmatūru. Tika veikta arī
jutīguma analīze, un rezultāti tiek detalizēti izvērtēti, lai noteiktu, cik modeli ir imitēti
scenārijiem.

Šis darbs ietver 91 lappuses, 39 attēlus, 19 tabulas un 79 atsauces.

7
 TABLE OF CONTENTS
INTRODUCTION ....................................................................................................................13
1. ETHYLENE PRODUCTION AND MARKET ................................................................16
1.1. World Ethylene Market ............................................................................................. 16
1.2. The bio ethylene necessity ........................................................................................ 21
1.3. Life Cycle Assessment .............................................................................................. 21
2. NEW TECHNOLOGICAL PROCESS FOR BIOETHYLENE PRODUCTION .............25
2.1. Production of Bioethanol and Vinasse from sugar cane and other starch sources .... 28
2.1.1. Production process of Bioethanol from sugarcane in Brazil.............................. 30
2.1.2. Bio ethanol production process from corn crops ............................................... 36
2.1.3. Bioethanol production from other raw materials ............................................... 39
2.2. Methane Production from co-digestion in AnSBBR ................................................. 40
2.3. Oxidative Coupling of Methane (OCM) ................................................................... 42
3. LIFE CYCLE ASSESSMENT METHODOLOGY ..........................................................46
3.1. Goal Definition .......................................................................................................... 46
3.1.1. LCA System Boundaries .................................................................................... 46
3.2. Scope ......................................................................................................................... 48
3.2.1. Functional Unit .................................................................................................. 49
3.3. Limitations and assumptions ..................................................................................... 49
3.4. Life cycle Inventory (LCI) ........................................................................................ 50
3.4.1. Sugar Cane Production....................................................................................... 50
3.4.2. Sugar cane Juice Production .............................................................................. 52
3.4.3. Fermentation and Distillation Process ............................................................... 54
4. LCA RESULTS AND DISCUSSION ...............................................................................57
4.1. Life cycle data and interpretation .............................................................................. 57
4.1.1. LCA for sugarcane production ........................................................................... 59
4.1.2. LCA for clarified sugarcane juice production.................................................... 62
4.1.3. LCA for vinasse production ............................................................................... 65
4.2. Summary of LCA results ........................................................................................... 67
4.3. Sensitivity Analysis ................................................................................................... 69
4.3.1. Sensitivity to power consumption ...................................................................... 71
4.3.2. Sensitivity to the method.................................................................................... 72
CONCLUSIONS .......................................................................................................................75
RECOMMENDATIONS ......................................................................................................... 77
REFERENCES ......................................................................................................................... 78
ANNEXES ............................................................................................................................... 84

9
List of Figures
Fig. 1.1. Ethylene Production 2010 [Lewandowski, 2016] ......................................................17
Fig. 1.2. Ethylene production installed capacity additions and demand variation.
[Lewandowski, 2016]................................................................................................................17
Fig. 1.3. Ethylene Production from traditional sources (CTO and MTO) [Lewandowski, 2016]
...................................................................................................................................................18
Fig. 1.4. MTO/CTO Ethylene Derivatives (Merchant linked to EO/EB/PE). [Lewandowski,
2016] .........................................................................................................................................18
Fig. 1.5. (a) Prices of ethylene per market (b) Ethylene production cost. [Lewandowski, 2016]
...................................................................................................................................................19
Fig. 1.6. Regional Ethylene Gross Margin [Lewandowski, 2016] ...........................................19
Fig. 1.7. Representation of a product’s Life Cycle [Rebitzer, et al. 2004] ...............................23
Fig. 1.8. Flowchart for OCM Process. Own preparation according to [Stünkel, et al. 2012]...24
Fig. 2.1. EMP glycolysis pathway. Own preparation with information from Bai, et al., (2008)
and Aram & Taek, (2015) .........................................................................................................27
Fig. 2.2. Technological routes to produce bioethanol [Coordinacion BNDES y CGEE, 2008]
...................................................................................................................................................29
Fig. 2.3. Productivity for each different feedstock in the production of bioethanol [Coordinacion
BNDES y CGEE, 2008] ............................................................................................................30
Fig. 2.4. Sugar and sugarcane bioethanol basic production scheme [Coordinacion BNDES y
CGEE, 2008] .............................................................................................................................34
Fig. 2.5. Wet grinding process of production of bioethanol from corn [Coordinacion BNDES y
CGEE, 2008] .............................................................................................................................37
Fig. 2.6. Dry grinding process of production of bioethanol from corn [Coordinacion BNDES y
CGEE, 2008] .............................................................................................................................38
Fig. 2.7. Scheme of the AnSBBR with recirculation. [G. Lovato, et al. 2018] ........................42
Fig. 2.8. Mini-Plant for OCM process. Absorption CO2 column, membrane unit with absorption
column and membrane reactor. [Stünkel, et al. 2012] ..............................................................44
Fig. 3.1. System Boundaries .....................................................................................................48
Fig. 3.2. Sugar cane Production subprocess [Incauca, 2019] ...................................................51
Fig. 3.3. Sugar cane juice production subprocess [CGEE, 2009] .............................................53
Fig. 3.4. (a) Fermentation process, (b) Ethanol distillation process .........................................54
Fig. 4.1. Simapro Network for Vinasse Production from sugarcane. .......................................58
Fig. 4.2. Impact assessment characterization per impact category ...........................................59
Fig. 4.3. Impact assessment weighting per impact category .....................................................60
Fig. 4.4. Damage assessment in areas of concern .....................................................................61
Fig. 4.5. Impact assessment characterization per impact category ...........................................63
Fig. 4.6. Impact assessment weighting per impact category .....................................................63
Fig. 4.7. Damage assessment in areas of concern .....................................................................64
Fig. 4.8. Impact assessment characterization per impact category ...........................................65
Fig. 4.9. Impact assessment weighting per impact category .....................................................66
Fig. 4.10. LCA results weighted per areas of concern ..............................................................67
Fig. 4.11. Effect of each process in Global warming category .................................................68
10
Fig. 4.12. Effect of each process in Land Use category ........................................................... 68
Fig. 4.13. Process influence in relevant Impact categories ...................................................... 69
Fig. 4.14. LCA comparison between bioethanol and Vinasse production ............................... 70
Fig. 4.15. LCA interpretation (a) weighted results. (b) single score ........................................ 71
Fig. 4.16. Characterization Results for vinasse production using EDIP2003 .......................... 72
Fig. 4.17. Weighted results for impact categories using EDIP2003 ........................................ 73
Fig. 4.18. Global warming results comparison across models ................................................. 74
Fig. 4.19. Ozone layer depletion results comparison across models ........................................ 74

11
List of Tables
Table 1.1. Equivalent Trade Flow of Ethylene .........................................................................20
Table 1.2. Oil producers in Latin America ...............................................................................20
Table 2.1. Types of energy used in the production of bioethanol with sugarcane (Coordinacion
BNDES y CGEE, 2008) ............................................................................................................36
Table 3.1. Typical cycle of sugarcane in Brazil (Macedo, et al., 2004) ...................................49
Table 3.2. Sugar Cane Production LCI .....................................................................................52
Table 3.3. Sugar cane juice production – LCI ..........................................................................53
Table 3.4. Fermentation and distillation processes - LCI .........................................................55
Table 4.1. Life cycle data for GHG in Sugarcane production stage .........................................59
Table 4.2. Damage assessment for sugarcane production ........................................................60
Table 4.3. Life cycle data for land use in Sugarcane production stage .....................................61
Table 4.4. Life cycle data for human health in Sugarcane production stage ............................62
Table 4.5. Damage assessment for sugarcane juice production ................................................62
Table 4.6. Life cycle data for human health in Sugarcane juice production stage ...................64
Table 4.7. Life cycle data for GHG and land occupation in Sugarcane juice production stage
...................................................................................................................................................65
Table 4.8. Damage assessment for vinasse production (F.U.) ..................................................66
Table 4.9. Life cycle data for human health in Vinasse production stage ................................67
Table 4.10. Life cycle data for GHG and land occupation in Vinasse production stage ..........69
Table 4.11. Damage assessment for Vinasse production (F.U.) ...............................................72
Table 4.12. Characterization of impact assessment EDIP 2003 ...............................................73

12
 INTRODUCTION
In the seeking for different strategies to achieve greenhouse gases (GHG) emissions
reduction, bio-based fuels are gaining importance when compared with petroleum-based fuels.
But biofuels are only one part of the strategy. Biopolymers have started to also been considered
as they can either possess a faster biodegradation rate or been produced by renewable resources
in which case, it would theoretically release a lower amount of GHG per kilogram produced.
Some pathways to manufacturing different bioplastics exist nowadays, but since ethylene
is one of the main precursors for a vast range of plastics, it is important to search for an
economically feasible way to produce it. With the wide expansion of bioethanol production
from sugar cane and other sugar-rich crops, the ethylene use for producing synthetic ethanol
dropped in the 20th century, and now the reverse process became an alternative for bio-ethylene
production as according to Broeren, (2013), ethylene and bio ethylene are chemically identical
allowing the use of bio-based ethylene in existing equipment at the facilities. This process is
known as catalytic dehydration of ethanol and it has become in one of the main paths for bio-
ethylene production, especially because of the use of renewable feedstock for the bioethanol
production, aiding also in the capture of carbon dioxide from the atmosphere.
But one of the obstacles for this pathway is the number of wastes and co-products
bioethanol production process from these renewable feedstocks has. Even with the use of Best
Available techniques the ethanol yield in such processes has risen up to 95% from the chemistry
perspective, the final rate composition in the outflow for ethanol is up to 12% leaving as mainly
co-product a liquid stream that until now is widely used only as fertilizer plus irrigation source.
The result of this, is an allocation price for a whole process in only 10-12 % of the resulting
products, making bioethanol per liter a very sensitive commodity to any changes in prices for
raw materials, thus, a potentially expensive precursor for bio-ethylene production.
However, some studies have found a way to give to a wide variety of biological residues
used in the industry. Methane production by anaerobic digestion is one of them. This process
not only gives an economic benefit to industries like the dairy or bioethanol production but also
deliver a positive environmental impact by the production of biogas that can be a substitute for
natural gas needs. Biogas not only reduces the need for extractive activities but also, as it is
locally produced, it would not depend on imported oil or natural gas, reducing the pollution
associated to transport and upstream drilling activities. On top of that, production of methane
by co-digestion of two or more sources with high organic load, will also reduce the pollution in
waters bodies, caused today mainly due to the dumping of industrial and residential wastewaters
into them.
Moreover, most recently bio Methane is becoming the most important transitionary
feedstock for the main petrochemical products as Propylene and Ethylene. But methane as an
alternative feedstock for petrochemical manufacturing is not new, and it has been studied form
more than three decades (Keller & Bashin, 1982). The process was then defined as Oxidative
Coupling of Methane (OCM) and through time has been investigated, trying to find the most
suitable parameters to meet commercial costs and yield when compared to the steam cracking
via.
As will be discussed, the ethylene market is expected to keep growing, leaving South
America market under a trade flow imbalance, making necessary to increase the ethylene
production in the following years. As Bioethanol yield from sugar sources has already reached
values above 95 %, manufacturing of bio-ethylene via catalytic dehydration of bioethanol
would require an increase in installed capacities and expansion in the land use towards sugar
and starch crops, finally resulting in a higher amount of co-products been either dumped into
water bodies or directly to the soil. This brings to light the urgent necessity for new bio ethylene
production process that does not require further land use works under a cleaner production
13
philosophy, by the recycling of wastes and new technologic techniques ensuring the shrinking
in GHG emissions and other environmental impacts.
During this work, a Life Cycle Assessment for the production of Bioethanol/Vinasse from
sugarcane crops is performed, as part of a bigger project to calculate the total environmental
load of a new biorefinery in Brazil where Vinasse and other domestic or industrial wastes and
wastewaters will be used as raw material for anaerobic co-digestion to produce biomethane
which later would be used in an OCM process to obtain bio ethylene.
A comprehensive summary of all the technologies that are involved in this new proposed
bio ethylene production pathway are described in this Master Thesis to provide a full picture in
what could be considered a completely new cleaner production process comprising most of its
techniques.
Problem
Bio ethylene production from catalytic dehydration of ethanol although is considered to
have low-cost leaves as residue the vinasse obtained from the ethanol production, which can be
up to 10 L of vinasse per 1 L of bioethanol.
The use of vinasse resulting from bioethanol production has been restricted primarily to
fertigation, but this approach might compromise the soil structure and surrounding water
bodies. A higher economic benefit is required from this co-product to increase economic
feasibility for new facilities making it more attractive for investors.
The topicality of the work
The increasing demand for ethylene to fill the growing uses for its products, will result in
either increasing the production from its fossil sources and usual methods or the arising in the
bio ethylene production installed capacities. Either way the impact on the environment is an
issue as current bio ethylene production techniques involve the use of large amounts of arable
land and the disposal of wastewater in a non-sustainable way.
Aim of the work
To deliver reliable data for further environmental impact comparison for the whole
production process of Bio-ethylene via OCM method against ethylene conventional production
pathways.
Objectives
To determine the current environmental impact from bioethanol and vinasse production
in Brazil’s biorefineries without considering sugar production.
Calculate the environmental load in different Impact categories using simapro software.
Object
Assess the environmental impact of the Vinasee production in Brazil using sugarcane as
main raw material.
Hypothesis
Production of vinasse and bio ethanol has a low environmental impact constituting a
feasible option for the production of bio ethylene by OCM.
The novelty of the work
Previous Life Cycle Assessments regarding the production on Bioethanol from sugarcane
and other starch sources have been previously done, considering theoretical values for raw
14
materials and using virtual biorefineries. In this work, real data from sugarcane crop fields in
Brazil and Latin-American have been used, considering state of the art technologies and Best
Available Techniques implemented in the latest and more recent facilities constructed.
The practical meaning of the work
Results from this work can be used in conjunction with LCA performed for AnSBBR and
OCM processes to determine the total environmental impact of a new bio ethylene production
model.

15
 1. ETHYLENE PRODUCTION AND MARKET
Being the first member of alkenes, ethylene is a colorless gas with a boiler point of -103.7
⁰C at normal atmospheric pressure (Zimmermann & Walzl, 1997). Ethylene is a compound very
reactive in the presence of other chemical agents and its barely soluble in water and alcohol. As
mentioned by Zimmermann & Walzl, (1997), it is also the main precursor for many other
compounds, ethylene by direct or indirect hydration can produce ethanol, straight olefins chains
can be obtained by oligomerization and these longer hydrocarbons are then used as
comonomers for manufacturing low-density poly-ethylene, producing synthetic lubricants,
diesel gasoline, detergents and other grades of polyethylene among a variety of chemical bases
(Matar & Hatch, 2001). All this is possible because ethylene is a good starter molecule due to
the double bond and its simple chemical structure. One more of the main intermediated obtained
from ethylene is ethylbenzene, which is obtained by alkylation and it is the precursor for styrene
production. Styrene is used as raw material for polystyrene production, used for insulation, the
rubber in tires, footwear and packaging (Zimmermann & Walzl, 1997). This is why ethylene is
probably the most important product in the petrochemical industry due to the yield into many
intermediate and final products such as resins, plastics, solvents, fibers, elastomers, and anti-
freezers. By 2016 the ethylene demand was 146 Mton mainly driven by polyethylene market
demand, its main sub-product.
Ethylene is mainly produced by steam cracking, a process that uses as feedstock a variety
of hydrocarbons and by catalytic cracking of light gases. When produced via pyrolysis from
Naphtha, the yield can be as high as 35 % but when ethane is used the yield rises up to 80 %
(Matar & Hatch, 2001). The use of ethane has also increased as it can be obtained from Natural
gas, which availability has arisen in the last decade, due among other things, to the deployment
of hydraulic fracking technology (Holloway & Rudd, 2013), causing ethane price to drop as a
result of the abundance of this raw material. Nevertheless, Holloway & Rudd (2013) and Bame
& Fehler (1986), have performed studies showing the environmental damage, hydraulic
fracking might cause to underground water sources and even increase seismic activities.
Also, both these processes are highly dependent on petroleum extraction and downstream
activities which lead to important CO2 emissions and conflict with the aim for reducing fossil
fuel consumption and climate change mitigation. As oil resources are declining or its production
is being affected by market volatility, the large reserves of shale gas, the arising availability of
Biogas from landfills and biodigesters; other paths for ethylene production has been studied
during the last century.

1.1. World Ethylene Market

In the world, ethylene is produced mainly from Naphtha (43 %) as it is the easiest to
transport and is used mainly in Europe and Asia. Ethane, on the other hand, is used as a raw
material in the Middle East and North America, where crude oil is found along with Natural
Gas (Lewandowski, 2016). Ethylene market can be said, is well balanced as capacity additions
have been able to supply the increasing worldwide demand (Fig. 1.1).

16
 3%

6% 4%
27%
11%

12%

20%
17%

North America Middle East NE Asia SE Asia

Wester Europe India South America Other

Fig. 1.1. Ethylene Production 2010 [Lewandowski, 2016]

But installed capacity does not always mean production or ability to supply the demand,
and furthermore, according to Lewandowski (2016), annual demand increase is going to
overtake the Capacity additions due to delayed and reduced projects (see Fig. 1.2).

14
12
Million Metric Tones

10
8
6
4
2
0
-2
2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020 2021

North America Middle East Others

West Europe Asia Annual Demand Increase

Fig. 1.2. Ethylene production installed capacity additions and demand variation.
[Lewandowski, 2016]

In 2016, there were four main feed type for conventional ethylene production, those
shares are believed to change reducing naphtha participation and increasing the ethane and
unconventional (MTO and CTO) feedstock (Fig. 1.3). This phenomenon is not only due to
changes in feed availability but also in an increase in the complexity of the ethylene value chain
as demand drivers are also changing. Some of the supply processes for ethylene production are:
o Oxidative coupling of Methane
o Coal to Olefins Process
o Methanol to Olefins Process
o Traditional feeds (LPG and Naphtha)

17
 2016 2021
6.4% 8.8%

14.8% 42.6% 13.6% 38.6%

36.3% 39.0%

Naphta Ethane Other LPG Naphta Ethane Other LPG

Fig. 1.3. Ethylene Production from traditional sources (CTO and MTO) [Lewandowski, 2016]

Ethylene’s demand is highly dependent on its products market, as it is the raw material
for many industrial products such as Polyolefins (PE/PVC/PET), Coal to MEG, Coal to VCM
among others.
It is because of this that world capacity has increased in the last two decades, coming
from 105.8 Mton in 2001 to 165 Mton in 2016 and has been estimated to keep growing up to
195 Mton for 2021. The process used for Ethylene production and raw material feed is also
driven by its derivatives market as can be seen in Fig. 1.4, CTO process main product are HDPE
and on the other hand, the MTO process delivers a wider range of products.

MTO-Ethylene Derivatives CTO-Ethylene Derivatives

Ethylene EDC
Oxide 4%
27%

HDPE
43%

EDC
10% Merchant HDPE
20%
96%

Fig. 1.4. MTO/CTO Ethylene Derivatives (Merchant linked to EO/EB/PE). [Lewandowski,

2016]

The production costs of ethylene can vary regarding the region and the type of raw
material used. For instance, while in 2016 the ethylene cost in the USA was near to 200
USD/metric ton (from ethane), in West Europe was close to 500 USD/metric ton (naphtha), and
850 USD/metric ton in China if MTO process was performed. Fig. 1.5 shows production costs
depending on the main Raw Material used per region, and the ethylene price in the markets for
the last ten years and the prognosis up to 2021.

18
 (a) Regional Ethylene Prices (b) Regional Ethylene Cost
2000 1500

USD per Metric Ton

USD per Metric Ton

1000
1000
500
0 0
2008 2013 2018 2008 2013 2018

US Acqisition Price WEP Contract Price US Ethane WEP Naphtha

SEA Spot Price SEA Naphtha

Fig. 1.5. (a) Prices of ethylene per market (b) Ethylene production cost. [Lewandowski, 2016]

Fig. 1.6 shows how the changes in production costs depending on the Raw Material per
region and its price have driven different gross margin per market. It is clear how this is an
attractive business that has been estimated to keep growing up to 11.6% (TechSci Research
report, 2016) until 2025 driven by the packaging industry and further applications within the
building and construction sector and the automobile industry.
For the last 6 years the automobile production growth 13.7%, which increased the
ethylene derivatives demand and such a trend is expected to continue until 2025.

1000
900
800
USD per Metric Ton

700
600
500
400
300
200
100
0
2008 2010 2012 2014 2016 2018 2020

US WEP SEA

Fig. 1.6. Regional Ethylene Gross Margin [Lewandowski, 2016]

Looking towards the expected growing market for Ethylene, it is then necessary to look
at how the regional markets are fulfilling their necessities for this important raw material in the
Chemistry Industry. As can be seen in Table 1.1. Equivalent Trade Flow of Ethylene, the
Middle East is leading the World Market production thanks primarily to Saudi Arabia Basic
Industries Corporation (SABIC) followed by North America with the capacity additions in the
last 5 years at Dow Chemical Company and Exxon Mobil Corporation mainly.
As can be seen, South America and Northeast Asia Regions are going to be the most
affected in terms of commercial balance according to the forecast of Lewandowski, (2016) for
ethylene in 2021. This must be an alert for local governments all alongside these regions.

19
Table 1.1. Equivalent Trade Flow of Ethylene
Ethylene Equivalent Trade flow (metric tons) 2011 2016 2021
North America 5228 6220 13281
South America -2858 -2583 -3803
West Europe -384 307 -1305
Middle East 13953 17952 19606
Northeast Asia -8321 -10575 -14522
Southeast Asia -412 -953 -1931
Others -7382 -10455 -11446

Ethylene production in South America is not showing the same behavior as North
America or West Europe with additions in capacity every year. One of the main reasons is the
reduction in oil and gas production in the continent. With the last price oil crisis, countries as
Peru, Argentina, Colombia, and Ecuador reduced their Barrels of Oil per day Production
(BOPD) and the social and economic crisis in Venezuela has taken the country from 3 million
in 2005 to 2.2 M BOPD by 2017 (see Table 1.2).

Table 1.2. Oil producers in Latin America

South America greater Producers BOPD (millions)
Venezuela 2.2
Brazil 2.1
Mexico 1.9
Colombia 0.715
Ecuador 0.6

Keeping in mind that most of the produced oil in these countries is sold to Unite States or
China, and EEUU has built 17 million tons per year new facilities from 2012 to 2017
(Scodelaro, 2017) and 5 more running projects are going to add an additional 1 million, South
America needs to find an alternative raw material for ethylene production, as most probably,
local governments are going to keep selling their oil instead of using it for the local
petrochemical industry. Furthermore, the recent oil crisis showed the lower the oil barrel price,
the lower the production, as it becomes less profitable for the oil state companies, meaning less
raw material for the petrochemical processes, as is ethane derived from natural gas the main
used one and 75 % of this one comes from oil wells. The same scenario was observed by
Scodelaro (2017), for ethylene coming from naphtha especially in Brazil and Argentina where
most of the petrochemical plants are using naphtha and this one is linked to the oil production
instead of natural gas. Nevertheless, some governments like the Argentinean are trying to create
new incentives for investments in non-conventional gas sources due to new discoveries like the
one in Vaca Muerta with the second largest shale gas reservoir in the world. Such incentives
are as great as a fixed premium price of 7.5 $USD for 1 million BTU in 2018 down to 6.0 USD
in 2021.
Therefore, some companies are evaluating new alternative technologies from the cracking
process, using derivatives raw materials as oil prices have shown a great instability in the last
4 years, and although low prices reduce naphtha’s cost for cracking (see Fig. 1.5) to almost the
same as ethane’s, macroeconomic uncertainty is a great deal nowadays mainly due to Brexit
effect and economic war between USA and China.

20
 1.2. The bio ethylene necessity
As CO2 levels have increased from 280 ppm in 1750 (before industrial times) to 406 ppm
(Earth System Research Laboratory, 2018). Brazil for instance, as the biggest economy in Latin
America, has shown an increase in CO2 per capita from 0.65 to 2.59 metric tons in the last 56
years (The World Bank, 2018) mainly due to its economic growth and dependence on fossil
fuels to accelerate its economy. As the chemical Industry is one of the sectors with the higher
energy intensity with 16% of total global CO2 (Ravanchi & Sahebdelfar, 2014) emissions it is
important any additional capacity installed for chemical intermediary’s process such as ethylene
production, not only aims to supply the demand but also to be sustainable within the near future.
As said before, steam cracking is the conventional process to produce ethylene, and the
feedstock may vary in a wide range of hydrocarbons. Also, it was mentioned how while in
North America and the Middle East the main supply is light hydrocarbons, in Europe and Asia
steam cracking is conducted using a mixed Petroleum portfolio. As no matter where steam
cracking is performed, fossil fuels are used for producing ethylene, high amounts of CO2 are
released, and this causes a major concern in nowadays sustainable development business.
Therefore, substitutes for hydrocarbons are being explored to reduce the associated
environmental impact in ethylene production. Furthermore, the market pressure to cover the
steady but soon growing demand for ethylene in developing markets as South America and
Asia the environmental impact of steam cracking must be considered.
As ethylene is the raw material for many polymers, and the production of biopolymers is
under strong incentive due to either the fact of being biodegradable under certain conditions or
being produced from renewable materials (De Andrade, et al., 2013), it becomes necessary to
look for other sources for ethylene production, such as CO2 , biomass or bio-waste. Sustainable
development from a holistic approach has been gaining room within the academic field because
of the inclusion of the social, economic and environmental aspects. As explained before, the
economic forecast for the ethylene market is expected to keep growing as the demand for
plastics does not seem to decrease in the short term despite the efforts of some countries for
encouraging reuse and alternatives to plastic use. This, added to the shortage of oil and
hydrocarbons precursors necessary for the cracking, CTO, MTO or catalytic pyrolytic
processes, the environmental impacts from hydrocarbons extraction such as the ones observed
in 2017 in Vaca Muerta, Argentina where several NGO’s have reported hundreds of
hydrocarbons leaking events, pushes local economies in Latin America, on the seeking for
alternative routes on the ethylene obtention chemical process to be able to support at least a
large part of their own consumption (see Table 1.1).
From the social approach, as it has happened with bio ethanol production, the second and
third generation is expected to become commercial at large scale to avoid conflict with food
production and should be highly taken into consideration when deploying these kinds of
projects into countries with developing economies or scarce fertile land or food resources.

1.3. Life Cycle Assessment

Life cycle assessment comes as a response to a needed quantitative tool that gives the
possibility to identify the possible week parts to be strengthened and a holistic approach by
focusing not only of course at the production stage but also during the design phase. There are
two different approaches when modeling an LCA, attributional and consequential.
o Attributional. LCA modeling frame that inventories the inputs and output flows
of all processes of a system as they occur, it is comparative and retroactive.
Attributional modeling is chosen when one wants to know the environmental
impact of a product or function and the hotspots in its life cycle, or when it is
21
 desired to compare the impacts of two products with the same functional unit.
All environmental inputs and outputs are summed from raw material extraction
(cradle) to the gate of the product’s or function’s supplier or the waste treatment
facilities (grave). The result of attributional modeling is, therefore, often referred
to as an environmental footprint (or carbon footprint, water footprint, etc.).
Foreground system is the purpose of identifying where specific data should be
used versus where average or generic background data can typically be used by
default ("specificity perspective"). the foreground system is defined as those
processes of the system that are specific to it. processes are hence those that are
under the direct control of the producer.
o Consequential. LCA modeling principle that identifies, and models all processes
in the background system of the main system in consequence of decisions made
in the foreground system. It supposes changes in future; thus, this approach is
comparative and retroactive. It is highly used for waste management when
comparing incineration vs recycling. Includes secondary consequences and
market constraints so there and effect on the background systems.
Background system is the purpose of identifying which processes can be
managed by direct control or decisive influence from the point of view of the
decision-context of a study ("management perspective"). The background
system is then those processes, where due to the averaging effect across the
suppliers, a homogenous market with average (or equivalent, generic data) can
be assumed to appropriately represent the respective process. Those processes
that are operated as part of the system but that are not under the direct control or
decisive influence of the producer of the good
It is sometimes argued that the time-horizon "future" would be associated with
"consequential modeling", while the "past" with "attributional modeling". However also future
attributional data can be of interest (e.g. when extrapolating national, annual accounting data)
as well as retrospective consequential modeling. This latter case is of only theoretical interest.
Life Cycle Assessment (LCA) is the widespread tool to measure and compare in a
quantitatively way, impacts from different activities or process resulting in products such as the
one under study. As every single product has a life (Fig. 1.7) from its conception and design
through resource extraction, transporting, production or manufacturing, distribution or
commercialization of the product, consumption and final disposition.
All these activities, that are needed for the production of determined good, have
environmental impacts related to the resource consumption, emissions to the environment and
environmental exchanged (Rebitzer, et al., 2004). Life Cycle Assessment is then, a
methodological concept and method for calculating within an acceptable accuracy, the
environmental impacts caused directly by the lifetime of a product. Among those impacts, but
not limited to, are found “climate change, stratospheric ozone depletion, eutrophication,
acidification, toxicological stress on human health and ecosystems, depletion of resources,
water use, land use, and noise” (Rebitzer, et al., 2004).

22
 Fig. 1.7. Representation of a product’s Life Cycle [Rebitzer, et al. 2004]

When performing LCA in the obtention of bio ethylene from sustainable feedstocks, some
studies have been conducted already taking into consideration mainly the geographical
boundaries as it is the most determinant factor. For instance, according to Xiang, et al. (2014),
Coal to Methanol to olefins (CTO) in China is economically competitive and can replace
naphtha steam cracking, which is of high value for the region as China has large coal reserves;
the downside is LCA has proved CTO has higher energy consumption and greenhouse gases
released from its process are also larger. The United States of America for instance, with their
large shale gas reservoirs, has started to produce ethylene from steam cracking shale gas but
the GHG emissions have been a bit higher than steam cracking from conventional NG (He &
You, 2016).
There are already LCA studies for estimating the impact coming from corn and cassava
as raw materials as can be seen in paper from Hong, et al. (2014), and some other studies to
assess the impact of ethylene production via gasification and fermentation (Liptow, et al.,
2015). As these studies have different system boundaries, allocation methods and functional
units, Zhao, et al. (2018) performed an evaluation where a comprehensive CO2 analysis could
be performed taking into account several pathways for ethylene production including catalytic
pyrolytic process and the most interesting to comparing with, Bioethanol to ethylene route. This
Bio ethylene is obtained when biomass is transformed into Bioethanol by fermentation or
gasification of different renewable sources. These sources can vary from biomass crops like
sugar or starch, lignocellulose material and algal biomass which are also the main
representatives for the so-called first second and third generation of bioethanol. Usually, when
Bio-ethylene term is used, refer to lignocellulose route as this one avoids moral constraints due
to human food competition.
When (Zhao, et al., 2018) analyses the Bio-ethylene production by the bioethanol to
ethylene route and uses LCA to compare it with more traditional ways for ethylene production
such as MTO, steam cracking from petroleum (SCP), coal to methanol (CTO) and biomass to
methanol among others, it was found that while SCP pathway releases 1.7 CO2 ton per ton of
ethylene produced, CTO emissions are as high as 8.5 CO2 ton/ton of ethylene and biomass to
23
methanol releases -1.3 CO2ton/ ethylene ton, Bioethanol to ethylene route only releases -0.6
tons of CO2. In this last route, biomass is transformed into ethanol by fermentation and then
into ethylene by dehydration under controlled temperature and the presence of a catalyst. But
there are many other ways that might be still without assessing, and one of them is the Oxidative
Coupling of Biomethane (OCM) obtained from Biogas coming from a previous fermentation
process.
OCM is (Stünkel, et al., 2012) a promising alternative to petrochemistry as it is a process
where a natural or biogas can be used to obtain Green ethylene or liquid fuels. The main reaction
and the undesired one that has limited the yield and brought high separation costs for the by-
products are presented in Eq. 1 and 2.
As seen in Fig. 1.8, in the first reaction the two reactants (methane and oxygen) are
distributed into a usually fixed bed or fluidized bed reactor with a determine catalyst, where
ethylene is formed. Ethane, CO2, and H2O are also formed as co-products and then are separated
in the downstream sections that consist of two separation units, one for phase separation and
the then one for carbon dioxide removal. In the last stage products, separation is carried out.

Fig. 1.8. Flowchart for OCM Process. Own preparation according to [Stünkel, et al. 2012]

So far, this process has not been yet implemented on an Industrial level due to the low
yield compared with usual mentioned methods and the cost and complexity for separation of
the co-products to obtain a polymer grade product. Another problem with the OCM production
way is that so far, all developed catalysts do not meet the expectation regarding yield and
production cost for the commercial-scale application.
However, in a new approach proposed by Stünkel, et al. (2012), it was found that
equilibrium among high selectivity and high methane conversion can be achieved if the right
reactor for the OCM process is selected in junction with the properly designed catalyst. This
new method brings a possible new alternative for green ethylene production that could not only
help in the struggle to come for some regions in terms of market supply but also in reducing the
environmental impact from this usually pollutant but needed production process in the
humankind lifestyle, that seems to keep pushing for ethylene derivative products.

24
 2. NEW TECHNOLOGICAL PROCESS FOR BIOETHYLENE
PRODUCTION
As Greenhouse gases emissions have become the point of attention in the world due to
the climate change and chemical industry is responsible for 16% of total CO2 emissions to the
atmosphere, the pressure for finding new alternatives, other than steam cracking for ethylene
production has arisen in the last years. Many alternatives have been studied to find alternative
routes and feedstocks in order to come with a sustainable road map for low environmental
impact in the olefins industry. Furthermore, the cracking process for ethylene production
requires temperatures between 600 – 1000 ⁰C which means a high energy demand and a steady
low price of Hydrocarbons (Yu, et al., 2010).
De Andrade, et al. (2013), mentioned that ethylene monomer obtained through non-
conventional pathways using renewable sources, is chemically identical to the monomer
obtained via steam cracking or other petrochemical routes, hence, bio ethylene can be used in
the production of Polyethylene (PE) as there is no need for replacement of equipment,
procedures or process conditions in the facilities. This polyethylene is known as green
polyethylene. Industries depending on PE might replace it by green PE as it has the same
properties and features as the fossil version.
Subsequent, bio ethylene can also be obtained from many raw materials such as plants,
microorganisms, and by catalytic dehydration of ethanol. In nature, ethylene controls some
events in the lifecycle of plants, it can be sense and produced by them and it is known as the
plant hormone. This pathway is called ethylene biosynthesis (Yang & Hoffman, 1984). In the
middle of the last century, some bacteria and fungus capable of producing ethylene were
discovered (Young, et al., 1951). Recently, Xiong, et al. (2015), proved ethylene could be
produced from cyanobacteria in an efficient and sustainable way by the cyanobacterial
tricarboxylic acid cycle of the recombinant cyanobacterium. As claimed by Hong and Nielsen
(2012), in the near future the production of bio-ethylene by using microorganism will be an
important alternative to the steam cracking way or other conventional routes, as this technology
is still in the early stages of development. Due to this, a techno-economic assessment performed
by Markham, et al. (2016), found that great improvements in reactor design and separation
technologies must be conducted for the cost to drop and become a feasible path for bio ethylene
commercial production.
But it is the catalytic dehydration of ethanol the preferred way when bio ethylene is
intended as there have been commercial production plants built since the middle of the 20th
century. This process consists of two catalytic reactions, each of one competing for the ethanol
dehydration. In the first one (Eq. 1), intra-molecular dehydration occurs from ethanol to
ethylene endothermically, while in the second one, ethanol is yield into diethyl-ether
exothermically (Eq. 2). As the yield towards ethylene increases between 300-500⁰C (Abas, et
al., 2017) and diethyl-ether is obtained at lower temperatures, it has become of high importance,
finding a catalyst with high catalytic activity towards ethylene at a lower temperature, to reduce
the energy demand in the process (Yu, et al., 2010).
𝑐𝑎𝑡
𝐶2 𝐻5 𝑂𝐻 → 𝐶2 𝐻4 + 𝐻2 𝑂 + 44.9 𝑘𝐽/𝑚𝑜𝑙 (2.1.)
𝑐𝑎𝑡
2𝐶2 𝐻5 𝑂𝐻 → 𝐶2 𝐻5 𝑂𝐶2 𝐻5 + 𝐻2 𝑂 − 25.1 𝑘𝐽/𝑚𝑜𝑙 (2.2)

These dehydration reactions occur in the vapor phase of the reactor, which can be a Fixed
bed reactor that allows flexibility as the reaction can be done either at adiabatic or isothermal
conditions or fluidized bed reactor where ethanol conversion occurs at adiabatic conditions. In
both reactors, under proper and controlled conditions, the conversion of ethanol is higher than
25
97 % up to 99.5 % for the fluidized bed one, and the ethylene selectivity is around 95-99 % in
the fixed bed one, while 99.9% can be reached in the fluidized reactor (Abas, et al., 2017) and
(Morschbacker, 2009).
Regarding the catalyst, many solid ones have been studied Aguayo, et al. (2002) and
Valero-Romero, et al. (2019), been activated alumina base one of the first ones used for alcohol
dehydration, phosphoric acid based was the first one to be used in 1930s but due to deposition
of coke limiting the catalyst activation its use stopped in the 1950s decade. Molecular-sieve
catalyst provides a larger specific surface area and there are different types depending on the
molecular structure, known as ZSM-5 types, SAPO types, A-type and AM-11 type.
Unfortunately, these catalysts are very expensive due to the highly complicated preparation
process, can be deactivated easily and are less stable, although many studies as the one
performed by Yu, et al. (2010) are still been performed to find commercial alternatives for the
use of this type of catalyst as they present the advantages to operate at lower temperatures, and
catalyze ethanol form aqueous solution at low concentrations.
Current industrial plants for ethanol dehydration for bio ethylene are using mainly
Heteropoly acid catalyst type. This catalyst was studied for ethanol dehydration by Noritaka
and Makoto (1997), founding a high activity and selectivity for ethylene at relatively low
temperature.
Some of the by-products of dehydration reaction are Acetic acid, butane, butylene
isomers, ethyl acetate, acetone, methanol, methane, ethane, propane, propylene, carbon
monoxide, and carbon dioxide. Because of this, a purification process must follow the reaction
one, as ethylene is mainly used for polymerization of plastics and high purity is required to
ensure this reaction (Bergstra, 2004). Ethylene is purified in consecutive operations, starting
with the cooling of the stream and removal of most of the water formed alongside with
condensable polar substances such as unreacted ethanol, acetic acid, and acetaldehyde. The
dehydrated ethylene still containing small contaminant traces is then treated depending on the
desired purity for the final product. If polymer grade ethylene is desired, the ethylene stream is
caustic-washed in a scrubbing tower to take out carbon dioxide and then is compressed to pass
through a drying bed with molecular sieves to obtain the chemical grade with over 99% of
purity. Afterward, the chemical grade ethylene is fractionated in a cryogenic distillation system
to sequestrate any light and heavy materials to finally acquire the polymer grade
(Morschbacker, 2009).
Morschbacker (2009) conducted an economic assessment of the production of bio-
ethylene from bioethanol concluding this pathway is not economically feasible in most areas of
the world as ethanol price by that year was almost the same as the ethylene obtained by
petrochemical ways. In his study, a negative profit margin was found and a higher price for
ethylene would be needed to get a Net Present value equals zero. With current trends and
forecasted oil prices below 90 USD/bbl, is not likely this will occur in the coming years. But,
if biomass is used to produce ethanol, it turns out that bioethanol only accounts for 60 – 75%
of ethylene cost depending on the region.
The largest bioethanol producers in the world are the United States and Brazil, responsible
for almost 83% of the total supply. In the US for instance, where the ethanol price is 447
USD/metric ton (Trading Economics, 2019) and the ethylene spot price is estimated around 750
USD/metric ton (Fig. 1.5) the margin for the whole bio ethylene production including transport
is 40%. According to Morschbacker (2009), the transport cost of a metric ton of ethanol for
400km can be around 80US$ ton-1 leaving a margin of only 30% for the catalytic dehydration
process, which can be very expensive due to technological complexity and catalytic preparation
costs.
Haro, Ollero, and Trippe (2013), established, after studying several alternatives, that is
the Brazilian production of bioethanol from sugarcane and its production by the indirect
26
synthesis of syngas, the cost-competitive way for bio ethylene production. Moreover, the
integration of bioethanol production with an ethylene production unit would save energy and
costs.
Bioethanol production has been accomplished by fermentation of biomass using
glycolysis metabolic pathway (Embed-Meyerhof-Parnas or EMP pathway) (Bai, et al., 2008).
In the EMP pathway, one molecule of glucose is metabolized and two of pyruvate are produced.
Pyruvate is under anaerobic conditions reduced to ethanol by releasing CO2 (Madigan, et al.,
2000). To accomplish this, yeast cells must be used to guarantee the ATP consumption formed
in the glycolysis, otherwise, the intracellular accumulation of ATPs would inhibit
phosphofructokinase (PFK), one of the most important enzymes in the glycolysis process. Yeast
uses ATPs for its biosynthesis, which results in yeast cell growth, a necessary process coupled
to the bioethanol production. The EMP pathway in S. cerevisiae was described by Aram and
Taek (2015) and can be seen in Fig. 2.1 as follows:
ATP ADP
ATP ADP

Glucose -6-P Fructose -6-P Fructose -1-6-di-P

2 ATP 2 ADP

Ethanol Acetaldehyde Pyruvate Glyceraldehyde -3-P

Fig. 2.1. EMP glycolysis pathway. Own preparation with information from Bai, et al., (2008)
and Aram & Taek, (2015)

Other co-products are also obtained during the EMP pathway, but it is Glycerol the main
one with almost 1 % (w/v) yield. Among the other co-products that are found, organic acids
and higher alcohols which alongside with the yeast cell growth decrease the ethanol yield. At
Industrial level, the ethanol yield can reach values of 90-93 % of its theoretical value, leaving
a residual stream with 2 g/L and no more than 5 g/L of residual sugar (Ingledew, 1999). This
waste is also known as Vinasse.
Mainly two biomass sources are used today in what is called first generation bioethanol
technologies, sugarcane (sucrose) and corn-derived starch (glucose) (Aram & Taek, 2015).
Sugar cane is mainly used in Brazil and delivers the bioethanol lower production cost when
compared with corn feedstock pathway in USA or sugar beets in the European Union
(Morschbacker, 2009). As these feedstocks compete with the demand for human consumption
and animal feeds, lignocellulosic biomass (LCB) has been studied as a sustainable feedstock
alternative for biofuel industries, what is known as second generation Bioethanol. When using
LCB or 1st generation feedstock as corn starch, hydrolysis is required as a pretreatment in order
to release fermentable sugars. These sugars are a mixture of hexoses (mainly glucose) and
pentoses (mainly xylose), and the typical yeast used for fermentation, Saccharomyces
cerevisiae, is not able to metabolize xylose. In addition, hydrolysates derived from LCB, have
fermentation inhibitors like furfural, phenols and acetic acid that must be removed to enhance
microbial fermentation, increasing the complexity for the use of 2nd generation feedstocks
(Gray, et al., 2006). Recent studies have aimed for improving the ethanol production from LCB,
but the utilization of these sugar mix in LCB hydrolysates is still not available at industrial level
for ethanol production (Geddes, et al., 2011).
27
 Bioethanol and biodiesel are the most common produced biofuel, nevertheless, ethanol is
not the best option for blending fuel due to its hygroscopic nature and the fact the only has 70%
of gasoline energy content (Hansen, et al., 2005). Hence, the use of bioethanol for producing
bio ethylene with a higher added value is to be considered.
Due to previously mentioned restrictions, the global ethanol demand is mainly fulfilled
by the production of it from sugarcane and starch feedstocks (Bai, et al., 2008). However,
although ethanol production has reached conversion values of 90 – 93 % at commercial levels
considering the sugar availability, the concentration of ethanol is only 10-12 % in the final
stream when sugarcane or corn starch pathways are followed (Bai, et al., 2008).
The residual stream only contains sugar in a range of 0.1 – 0.2 % (w/v) and this cannot
be further depleted mainly because the strong inhibition on the yeast cells when ethanol
concentration reaches 12 %. Resulting wastewater also called Vinasse, corresponding to almost
90 % (v/v) is the main co-product from ethanol production and does not have many uses in the
industry so far. In Colombian and Brazil has been used as a Potassium source for the crop’s
plantation. But Vinasse is rich in micronutrients and organic content and has been used in some
studies for its bioenergy potential. Bittencourt, et al., (2014) found a feasible economic way to
produce biohydrogen and fatty acids from vinasse in Brazil while Harihastuti and Marlena
(2018), proposed the used of vinasse as raw material for methane production using an anaerobic
digestion process.
The study from Almeida, et al. (2017) using vinasse in an anaerobic co-digestion reactor
to obtain biomethane will be reviewed in this chapter. Later on, the use of biomethane in an
OCM process to obtain bio ethylene will also view reviewed.
A closer look at the mentioned processes involving sugarcane and corn starch raw
materials for bioethanol production are presented as follow.

2.1. Production of Bioethanol and Vinasse from sugar cane and other starch
sources
Through biological routes, bioethanol can be produced from any biomass that contains
significant amounts of starches or sugars. At present, there is a slight predominance of
production related to starchy materials (53% of the total), such as corn, wheat, and other cereals
and grains.
In these cases, the conversion technology begins, generally, with the selection, cleaning
and grinding of the grain. The milling can be wet, when the grain is imbibed and fractionated
before the conversion of the starch into sugar (wet way), or dry when this is done during the
conversion process (dry way). In both cases, the starch is converted into sugars by an enzymatic
process at high temperatures. In this case, the sugars released are fermented with yeasts, and
the resulting wine undergoes distillation for the purification of the bioethanol. In addition to
bioethanol, these processes generally involve various coproducts, which vary according to the
biomass used.
Considering the production based on sugar, as in the case of sugar cane or beetroot, is the
easiest process and involves fewer steps, given the fact that the sugars are available in the
biomass. Generally, the process is based on the extraction of the sugars (by means of grinding
or diffusion), which can follow directly towards fermentation. After fermentation, the wine is
distilled, as well as in the case of starch-based production.
Fig. 2.2 presents a comparison between the different routes for bioethanol production,
which shows how the indices of productivity per unit of cultivated area can be differentiated.
The results of the graph correspond to tillage under conditions of good productivity, which in
some of the cases may imply a high use of inputs.

28
 Fig. 2.2. Technological routes to produce bioethanol [Coordinacion BNDES y CGEE, 2008]

The industrial technologies implicit in the Fig. 2.2, for the conversion of sugars and starch
into bioethanol, can be considered mature and available, with the exception of those related to
the hydrolysis of lignocellulosic materials (2nd generation), now under development, also
adopted to obtain bioethanol from the cellulose part of the cane. For Sugarcane, a production
of 80 tons of cane per hectare, productivity of 85 liters of bioethanol per ton of processed cane,
and the utilization of 28% of the available bagasse, as well as half of the straw converted into
the cane, are considered (Morschbacker, 2009). These values may vary from region to region
in Brazil, with a maximum productivity of 7500 L per hectare (De Andrade, et al., 2013) (see
Fig. 2.3). Beets and corn present productivities of 5500 and 3500 L per hectare each
(Coordinacion BNDES y CGEE, 2008).
In 2011, 86 billion liters of ethanol were produced in the world, with the United States
and Brazil leading the production from corn and sugarcane respectively (Licht, 2006) and
(Walter, et al., 2014) with a 88 % of the world production. However, the United States is the
leader by far with 54.2 Billion of liters in 2011. These two main feedstocks are studied in detail
during this subchapter due to their importance in the bioethanol production market.
Currently, sugarcane plantations are widely dispersed in mainly the southern Brazilian
territory and cover almost 9% of the arable land of the country only behind of soybean and corn
crops. The principal production region is the southeast responsible for more than 85 % of the
total production. The state of Sao Paulo is the leader with 60 % of the manufacture. In 2011 this
region had 185 mills operating and milled 58 % of the total sugarcane produced delivering 15.5
Billion of Liters and 23.5 Mton of sugar representing 62 % of the country manufacture (CGEE,
2009).
The production system involves more than 370 plants, whose processing capacities vary
between 600 thousand and 7 million tons per year, for an annual average of 1.4 million tons.
There are three different types of sugarcane milling facilities in Brazil. A miller where sugar
and bioethanol are processed in an integrated process. This type of plants presents the advantage
of flexibility being able to adapt the main product to the market demand, increasing the
operational profits by the economy of scales.

29
 Sugarcane
TYPE OF PLANT

Beetroot

Corn

Manioc

Wheat

0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
LITER/HA

Fig. 2.3. Productivity for each different feedstock in the production of bioethanol
[Coordinacion BNDES y CGEE, 2008]

Then, there is the kind of distillery than only produces bioethanol, being the most
preferred to build in the latter years increased its number from 2004. In 2011 Brazil had 168
facilities of this type.
Finally, the third type, the less common with only 14 constructed in 2011, the refineries
producing only sugar. The harvesting of sugarcane combining the three types of facilities
reached levels of 3.7 Mton of sugarcane crushed in Brazil. However, since 2008 this country
has experienced a difficulty to increase the bioethanol production seen even some years even
reducing its value. Still, Brazil has managed to keep the first position in exporting ethanol to
the world and it is expected to remain as one of the large exporters in the medium term (Litch,
2011).
According to International Energy Agency (2011), it is predicted that the ethanol
production in Brazil by 2020 should be around 64 BL, (50 BL if drawbacks continue to be an
obstacle) to export at least 10 BL considering a world market of 200 BL in 2020.
Yet, the ethanol industry must overcome many challenges and the expansion in the
installed capacity must come from production diversification and increasing productivity and
sustainability. This includes the development of second-generation biofuels at industrial levels
and the replacement of bioethanol as a precursor for ethylene production by other more
sustainable feedstocks.
The aim of this Master Thesis is to assess currently environmental load from the
production of bioethanol from sugarcane in Brazil considering a distillery type that only
produces bioethanol. This, within a larger objective of assessing the production of bio-ethylene
using the main coproduct obtained in Brazil from sugarcane refineries.

2.1.1. Production process of Bioethanol from sugarcane in Brazil

Sugarcane is a semi-perennial plant with the photosynthetic cycle of type C4, belonging
to the genus Saccharum, of the grass family, composed of perennial tall grass species, native to
warm temperate regions of Asia, specifically from India. The aerial part of the plant consists,
essentially, of the stems, in which the sucrose is concentrated, and by the tips and leaves, which
constitute the straw of the sugar cane.
Brazil presents two distinct harvest periods: from September to March in the North and
Northeast, and from April to November in the Center-South. This way, the country produces
bioethanol during the whole year, despite the fact that bioethanol production in the North and
Northeast region is only 10% of the national total, which was 22.5 billion liters in 2007. The
30
best distilleries produce approximately 85 liters of anhydrous bioethanol per ton of sugarcane.
The plants have production in about 71 kg of sugar and 42 liters of bioethanol for each ton of
processed cane in the combined distilleries.
Sugarcane is one of the world's major crops, cultivated in more than 100 countries
embodies an important source of rural labor in these countries. Despite this diffusion world,
about 80% of the world's production is concentrated in ten countries, being Brazil (455.3 x106
ton) the major producer followed by India (281.2 x106 ton) and China (100.7 x106 ton) (CGEE,
2009).
Notwithstanding the economic importance of sugarcane, its crop represents very little in
terms of land use, when compared to those crops dedicated to the production of grains with
food purposes. The area harvested from sugarcane in the world was approximately 20.4 million
hectares in 2006, while the harvested area of soybean was 93.0 million hectares, corn
corresponded to 144.4 million hectares, of rice, to 154.3 million hectares and the harvested area
of wheat was 216.1 million hectares.
In Brazil, sugar cane is the third largest crop in terms of land occupation, far behind corn
and soybeans due, in particular, to the excellent efficiency in photosynthetic conversion in the
conversion of the cane, which brings an outstanding average productivity, around 75 ton ha-1.
A production growth has befallen continuously with the deployment of flex-fuel vehicles,
launched on the domestic market in 2003. Sugarcane production has accelerated, to meet the
increased demand for hydrated ethanol approaching 520 million tons in 2007 (CGEE, 2009).
The ideal weather for cane cultivation is that which has two distinct seasons: one hot and
humid, to provide germination, tailoring, and vegetative development, followed by another cold
and dry, to achieve maturity and the consequent accumulation of sucrose on the stems.
Sugarcane does not have good productivity in climates such as the humid equatorial regions,
which is why the Amazon region does not have extensive commercial crops of this plant.
The bioethanol production can be divided into two phases, the agricultural and the
industrial phase. During the agricultural phase, several steps are carried on and will be explained
here.
The planting phase consists of the following operations: removal of dirty and cleaning of
the land, liming, sorting or plowing, terracing, distribution of fertilizer, seedling cover, spraying
of herbicide and furrows on the field.
These operations are carried out with the aid of specific equipment and implements. The
operation of seedlings distribution is still done manually in most cases, but mechanization has
advanced in recent years especially in the new facilities where biorefinery is integrated into the
crops field. There are two options of use for the cane planting season:
o 12-month cane: cane is seeded shortly after the last harvest and will be harvested
the next year; in this option, the land will always be cultivated with sugar cane,
but productivity is lower, hence this option is only adopted in about 20% of cases;
o 18-month cane: after the last harvest of the cane field, the soil is rested several
months or receives a culture rotation of peanuts, soy, sunflower or some vegetable
which helps to nitrogenate the soil; in this case, the productivity of the first cut is
much higher but there will be a space of about two years between the last cut of
the previous cycle and the first cut of the new cycle.
After the first cut, which corresponds to the so-called cane-plant, the sugar cane is
harvested on average four times from the regrowth of the cane cut.
An important feature of this production cycle is that, in the implementation of a cane
bioethanol production unit, agricultural activities must begin two or three years before the
industrial production, to multiply the seedlings and reach, after the beginning of the grinding,
stable production of raw material for three to four years. To try to reduce costs and preserve
soil fertility, techniques such as direct cultivation and the use of Controlled Traffic Structures
31
have been developed for agricultural operations, which allows for an increase in the number of
cuts, maintaining productivity levels elevated (CGEE, 2009).
Although there are records of cane productivity of up to 200 ton/ha (De Andrade, et al.,
2013), in the south-central region of Brazil - where most of the Brazilian plants are located - ,
the average productivity in harvested area is 82.4 t / ha, and in planted area (5 cuts, 6 years) is
68.7 ton/ha*year.
In a general way, the sugarcane agricultural productivity presents wide volatility which
occurs due to several factors, such as the characteristics of the planted variety, composition and
amount of the fertilizer applied, the physical-chemical properties of the soil, pests and invasive
plants, water availability and planting techniques, cultural and harvested crops. The complexity
of the biological and physical phenomena that participate in the interaction between the plant,
the soil and the environment makes the management of these factors take resources for
capturing and analyzing a large amount of data.
The treatment operations for the sugarcane crops depend on the type harvested and
specific situations of the cane field. The main ones are weed dressing (in case of cutting of raw
cane), fertilization and herbicide application. The application of fertilizers depends on soil
conditions, the productivity of sugar cane and other factors.
Usually, the use of vinasse and reduces the need for chemical fertilizers and improves the
organic matter content of soils. Vinasse is an industrial waste that, in the mid-1970s, was
discharged to water bodies such as streams, rivers, and open channels, causing environmental
damage. After studies, it was observed that vinasse presented a high concentration of nutrients
(such as potassium, organic matter, nitrogen), which can stimulate the use of this residue in
sugarcane crops, increasing sugarcane productivity and bring economic and environmental
benefits. The application of vinasse also represents an important source of water for the cops
and practically eliminates the need for irrigation.
Proper agricultural practices are essential for the sustainability of the sugarcane crop. This
area has evolved continuously with significant effects on production costs, productivity and
longevity of sugarcane plantations. The main points are: the development of equipment and
implements to reduce soils compaction, the correct application of fertilizers according to the
need of each field, a more rational and economic system for transportation of sugarcane, new
methodologies for some agricultural activities (seeding, fertilization and herbicide application),
new harvesting systems (mechanized avoiding the old burning method) and the use of chemical
ripeness at the beginning of the harvesting period. The burning method was replaced recently
in most of the sugarcane fields due to environmental restrictions. It is expected that in the year
2020, after the agreements signed between the government and the producers, all the cane is
harvested mechanically, without having to burn the cane fields (CGEE, 2009).
After cutting, the cane is transported as soon as possible to the plant, in order to avoid
losses of sucrose. With the exception of some companies that use river transport, the transport
system is based on trucks, with various possibilities: single truck, double truck, road train and
road trailer, whose load capacities vary from 15 to 60 tons. It is worth mentioning that the
logistics of sugarcane, related to everything that involves the operations of cutting, loading, and
transport, is evolving continuously, to reduce costs and reduce the level of soil compaction.
The harvest of sugarcane in Brazil is in rapid evolution, from the traditional harvesting
manual system of the entire cane with the previous burning of the sugarcane to the mechanical
harvesting system of cane chopped without burning the cane field. The main reason for this
transition is in Federal and State laws (for São Paulo) that establish schedules for the reduction
of the burnings in the cane fields.
The transportation of sugarcane has also evolved in recent years, mainly due to the work
of the Sugarcane Technology Center (CTC) in partnership with car manufacturers. The main
objective has been to reduce transportation costs and adapt to changes in the harvesting system.
32
The average transport distance (from the field to the plants) in the Center-South of Brazil is
around 25 km and has increased in the recent past, following the continuous increase in the size
of the crops fields (CGEE, 2009).
The cane cannot be stored for a long time once cut and the plants operate only during the
harvest period, regardless of whether they produce sugar or ethanol.
The initial stages of the process are similar in both cases, reception, readiness, and
washing and intend to condition the cane for further extraction of juice and reducing the bagasse
waste. When cane was collected manually, and it cuts consisted of the whole straw, it was
washed using near to 5000 L per ton of cane in order to reduce the impurities that would affect
the juicing process. With the mechanized harvesting, the cane is now cleaned dry by using
pressurized air on the cane. The main diagram for a common sugar and bioethanol production
facility is shown in Fig. 2.4.
From the feeding process, the cane is transported by belts to the desiccator. This
equipment, consisting of a rotor with oscillating hammers and a desiccator plate, stems the cane
and opens the cells containing the sugars, facilitating the process of extraction of these sugars
(at least 82% of the cells must be open for good extraction in the millers). The sugar extraction
can be performed by two different methods, milling, and diffusion, but as diffusion is not used
in Brazil it will be a disregard for this study.
The milling process consists of extraction of the broth by making the cane pass through
two rollers, with a pre-established pressure applied to them. The mill must extract the broth, as
well as bagasse, in the process, with a degree of humidity that allows its use in the boilers. This
fiber continues to the plant's power plant, where it is used as fuel. In some new units implanted
in Brazil, extraction by diffusion has been adopted, with expectations of obtaining advantages
from the energy point of view
The mill is usually made up of four to seven grinding cylinders in series. After passage
through the first of these grinders, the ratio of broth extracted drops approximately seven to
somewhere between 2 to 2.5, making it difficult to extract the residual broth. The method to
recover most of the sugar contained in the cane is called soaking and consist of water injected
into the cane layer between the last two grinders and the juice of each grinder is injected before
the previous one until the second unit. Normally, the broth extracted in the first grinder is sent
to the sugar factory due to the better quality, and the rest of the juice goes to the distillery for
ethanol production in case of a combined production plant. The efficiency of sugar extraction
varies from 94.0% to 97.5% and the bagasse moisture is around 50%.
The bagasse is produced in an amount ranging from 240kg to 280kg per ton of sugarcane
ground (Coordinacion BNDES y CGEE, 2008), and it is the only fuel used in steam boilers,
generating all the necessary energy for processing of sugarcane and still, producing a surplus
that varies, in most cases, between zero and 10 %. Currently, in most facilities, the steam exits
the boilers at a pressure of 22 bar and 300°C; under these conditions, it is expanded in
counterpressure turbines down to 2.5bar, delivering energy for the main mechanical equipment
in the facilities (choppers, desiccators, and water pumps feeding the boilers), as well as electric
power generators, which is supplied the industry processes. Steam at 2.5 bar as flue gas, is
adjusted to the saturation condition and sent to the process, providing all the energy required
for the production of sugar and ethanol.
The cane juice, after leaving the extraction process, still contains a number of impurities
that has to be reduced to a suitable quality for processing at the sugar or distillery plant. The
first step in this treatment is intended for the removal through sieves of insoluble solids (sand,
clay, bagasse, etc.), whose contents vary between 0.1% and 1.0%. The second step is the
chemical treatment, with the purpose of removing insoluble impurities that have not been
eliminated in the previous phase and the colloidal and soluble impurities; this process aims at
coagulation, flocculation, and precipitation of these impurities, which are eliminated by
33
sedimentation. A pH correction is also necessary to avoid inversion and decomposition of
sucrose.
The treated juice can be sent to the manufacture of sugar or ethanol. In the manufacture
of sugar, sulfating step is mandatory to inhibit reactions that cause a color change, coagulation
of soluble colloids, and precipitate formation CaSO3 (calcium sulfide) and to reduce the
viscosity. A more complete treatment of the juice involves the addition of lime, and subsequent
decantation, treatment similar to that used in the manufacture of sugar.
Once treated, the juice evaporates to adjust its concentration of sugars (180 – 220 g/L)
(Bai, et al., 2008), and eventually, it is mixed with the molasses (if a combined facility
producing sugar and ethanol is considered), giving rise to the most, a sugar solution and ready
to ferment. Then, the juice must be cooled down to 60⁰ usually by the use of heat exchangers
containing water in countercurrent to finally be sent to the fermentation and distillation process.
The most continues towards the fermentation tanks, where yeasts (unicellular fungi of the
species Saccharomyces cerevisiae) are added and fermented for a period of 8 to 12 hours, giving
rise to the wine, a fermented most, with a concentration of 8% - 12% alcohol (Bai, et al., 2008)
but considering the newest techniques used in Brazil, this concentration can reach up to 13 %
(CGEE, 2009). This tank system decreases the back mixing, reducing product inhibition.
According to Madson (2003), 4 to 6 tanks in series are able to achieve the best balance between
the capital investment and the ethanol fermentation kinetics. The flocked yeast is collected by
baffles in each reactor tank, allowing the broth to overflow into the next one. This yeast slurry
is circulated by a pump sending it to a heat exchanger to maintain the fermentation temperature
between 32-34⁰, then a small yeast stream is poured into the next reactor to maintain a proper
biomass concentration in a range of 40 – 60 g/L (Bai, et al., 2008).

Fig. 2.4. Sugar and sugarcane bioethanol basic production scheme [Coordinacion BNDES y
CGEE, 2008]

The main used fermentation process in Brazilian distilleries is the Melle-Boinot, whose
main characteristic is the recovery of wine yeast by centrifugation. In this way, after
34
fermentation, the yeasts are recovered and stored for a new use, and the wine is sent to the
distillation columns.
During the distillation, bioethanol is first recovered in a hydrated form, with
approximately 96° GL (percentage by volume), corresponding to about 6% water by weight,
leaving the vinasse as waste, in a proportion average of 9 to 15 liters per liter of bioethanol
hydrate produced. In this process, other liquid fractions are also separated, giving rise to the
second alcohols and fuel oil. Hydrated bioethanol can be stored as a final product or it can be
sent to the dehydration column.
But, since it is an azeotropic mixture, its components cannot be separated by simple
distillation. The most widely used technology in Brazil is dehydration through the addition of
cyclohexane, when a ternary azeotropic mixture is formed, with a boiling point lower than that
of anhydrous bioethanol. In the dehydration column, the cyclohexane is added at the top, and
the anhydrous bioethanol is removed from the bottom, with approximately 99.7 ° GL or 0.4 %
water by weight. The ternary mixture extracted from the summit is condensed and then
decanted, and the water-rich part is sent to the recovery column of cyclohexane.
Also, dehydration of bioethanol can be carried out by means of absorption with molecular
sieves or by extractive distillation with monoethylene glycol (MEG), which stands out due to
the lower energy consumption and the higher costs. Due to the growing demands of the external
market, several bioethanol producers in Brazil and other countries choose molecular sieves
since they are able to produce a less pollutant anhydrous bioethanol.
Considering the entire sugarcane bioethanol production process, the waste consists of
vinasse (between 700 and 900 liters per ton of cane processed for bioethanol), Glycerol, CO2
and other organic acids and higher alcohols. As mentioned before, in Brazilian plants these
residues are valued and then converted into sub-products, which are recycled and used as
fertilizers. In this way, the need to incorporate mineral fertilizers are significantly reduced and
the need for irrigation in the cane fields is avoided.
As the production of bioethanol implies a great elimination of water, the demand for
energy is high, mainly thermal energy, elaborated according to information from Pizaia (1998).
The steam demand for hydrated and anhydrous bioethanol considered, respectively,
conventional technology with a consumption of 3.0 kg to 3.5 kg of steam per liter of hydrated
bioethanol and the azeotropic distillation process with cyclohexane, with consumption of 1.5
kg to 2.0 kg of steam per liter of anhydrous bioethanol. About the demand for electric power,
there is a small variation between the processes, but all this approach the presented value of 12
kWh per ton of processed cane (see Table 2.1).
In the case of the bioethanol agroindustry based on sugarcane, all the energy consumed
in the process can be provided by means of a combined system of heat and power production
(cogeneration system), installed in the plant.
In the Brazilian case, considering the average values observed in about 60 plants in the
state of São Paulo, with the losses referred to a medium cane with 14% sucrose content
(Morschbacker, 2009). Based on these performance values, in the case of the exclusive use for
the production of bioethanol, with one ton of cane it is possible to obtain 86 liters of hydrated
bioethanol, while, those facilities which objective is a combined production of sugar and
ethanol can obtain 71 kg of sugar and 46 liters of hydrated bioethanol produced the molasses
(CGEE, 2009).
These last values are related to a process of production of sugar with two masses
(successive processes of crystallization), in which the honey is not used up, but the rest (which
contains enough sucrose) is sent to the production of bioethanol. This allows to improve the
quality of the product and decrease the energy consumption in sugar production. In short, the
synergies and possible complementarity between the production of sugar and bioethanol help
to reduce costs and improve the efficiency of agroindustry processes.
35
Table 2.1. Types of energy used in the production of bioethanol with sugarcane (Coordinacion
BNDES y CGEE, 2008)
Energy Unit Sugar Hydrated Pure
bioethanol Bioethanol

Thermal kg/ton 470- 370-410 500-580

sugarcane 500
(Like saturated vapor for boilers and
distilleries)

Mechanic kWh/ton 16 16 16
sugarcane
(Activation of preparation systems and
sugarcane grinding)

Electric kWh/ton 12 12 12
sugarcane
(Diverse variety of electric motors,
lightning, and other charges)

2.1.2. Bio ethanol production process from corn crops

There are two different processes that can be done in order to produce bioethanol from
starch, these are: dry milling and wet milling, the less popular in the industrial production being
the last one mentioned due to the fact that before the enzymatic hydrolysis of the starch
contained in the corn or wheat grains there must be a separation of the proteins and oils. On the
other hand, the process called dry milling, there is no separation of proteins and oils and the
whole grain is used for the production of ethanol, this leads to a co-product high in protein and
yeast that can be sold as animal feed and bring a positive economic effect to the ethanol
production. (Mohammad & Lennartsson, 2013).
Corn and sugar cane are C4 plants of the grass family that have a cycle of annual
production. Despite the fact that it is originally from Mesoamerica, nowadays corn is produced
in all countries with a production occupying 147million hectares. In this area in 2004, 725
million tons of corn were produced (Food and Agricultural Organization of the United Nations,
2008) giving this product high importance in human and animal food worldwide.
Producing almost half of the total worldwide volume, the United States is the leading
country in corn production. Additionally, it is the main raw material when producing bioethanol
in the country with a percentage of more than 98 % of the total amount produced coming from
corn. In an area of over 28 million hectares, in 2006 US production exceeded 267 million tons
of grains (US Department of Agriculture, 2008). 50 % of the total production was destined for
animal feeding, less than 20 % of its production is consumed by the bioethanol industry.
This plant is grown in temperate zones in spring, during April and May (in the case of the
United States) as this plant does not tolerate cold. Normally, a tillage rotation is required with
a nitrogen-fixing plant, which may be alfalfa or soybean (in regions of longer summers),
additionally, a third crop might be used, such as wheat. The land for this process should be
tilled every year in accordance with the traditional model notwithstanding, nowadays the tillage
is being taken to the minimum. Harvesting is usually done with mechanical harvesters and is
developed during the months of September till November (autumn in the US). During the

36
mechanized harvest, the straw and the corncob are left in the field, while the grains of the cord
is extracted after the ear of the steam is separated.
Around 9 tons of grains per hectare is the average productivity in the US (U.S.
Department of Agriculture, 2008). About 50 % of the dry matter of the plant is constituted by
the grains, in addition to the stem, leaves, straw, and corncob, totaling 15 tons of dry matter per
hectare. In order to preserve soil fertility, it is imperative to maintain a large part of the biomass
in the field that is harvested.
When comparing corn with sugarcane, it can be seen that the corn demands a larger
amount of fertilizers, these results deriving from areas with and without irrigation. In terms of
water, even though the cultivated area needs irrigation of less than 10 %, the total demand is
about 5.6 m3 per hectare. (NCGA – National Corn Growers Association, 2008).
Nowadays, the production of corn bioethanol can be done in two manners, called dry and
wet milling. This last one was the most commonly used until the 1990s (see Fig. 2.5), however,
the dry process is currently being most used worldwide (see Fig. 2.6). This is due to the fact
that thanks to the innumerable improvements made to the process, the investments and
operating cost has been dramatically reduced, reducing at the same time, the cost of the final
products, bioethanol.
Various co-products are recovered from the wet process as different fractions of the corn
grain are separated, co-products such as proteins, nutrients, carbon dioxide (CO2, used in the
soft drink industry), starch and corn oil. Starch (and consequently, bioethanol) is produced in a
greater volume, with approximate yields of 440 liters of bioethanol per dry ton of corns,
however, the most valuable product is the corn oil.

Fig. 2.5. Wet grinding process of production of bioethanol from corn [Coordinacion BNDES
y CGEE, 2008]
37
 On the other hand, if we talk about the dry milling, the only coproduct deriving from
bioethanol is a protein supplement that is used for animal feed known as DDGS (distillers dried
grains with solubles). Water and enzyme (alpha-amylase) are added to the ground kernels
during the process, in order to promote the hydrolysis of the starch in lower sugar chains. These
chains are saccharified by the action of glucoamylase in the next stage and the resulting product
is fermented. In order to reduce the pH and provide nutrients for the fermentation, in some units,
the liquefaction/saccharification undergo the recycling part of the fine vinasse (back setting
process).
The process of sugar release decreases its speed in a short time in spite of the fact that at
the beginning it is developed rapidly, this could lead to residence times in de reactor to change
from 48 to 72 hours in order to get the maximum saccharification of the starch. Saccharification
and fermentation are done simultaneously in many units in order to reduce the time and to avoid
any contaminations, leading also to a decrease in the conversion to glucose.
The glucose is transformed into bioethanol thanks to the action of Saccharomyces
cerevisiae yeast and the wine produced continues towards distillation, in the same way as in the
case of cane bioethanol. The resulting vinasse from this stage is then taken to a set of
centrifuges, where the fine vinasse is separated and may be reused in the process. The excess
vinasse is generally concentrated in evaporators and produce syrup of about 50 % moisture.
Afterward, the DDGS mentioned above is obtained by combining the syrup obtained with the
solids removed in the centrifuge and drying this to 10 % moisture.

Fig. 2.6. Dry grinding process of production of bioethanol from corn [Coordinacion BNDES y
CGEE, 2008]

All the remaining stages that are undertaken during this process are equivalent to the ones
in cane bioethanol production in Brazil, however, in the US the dehydration with a molecular
sieve is already the one that is most commonly used process when producing anhydrous
bioethanol. Generally, per dry ton of corn about 460 liters of anhydrous bioethanol and 380 kg
of DDGS are obtained.

38
 2.1.3. Bioethanol production from other raw materials
Another plant used is a native plant from Brazil that is also cultivated in tropical areas of
Asia and Africa, called Cassava. It is not only used as food in human and animal diets, but it is
also used and commercialized in Thailand and China and it is locally used for the production
of bioethanol for beverages. This plant provides some advantages like a high content of starch
in the roots, between 20 % and 30 %, the fact that it is easy to grow and it´s low edaphoclimatic
requirements leads to a production availability almost all year round.
When producing bioethanol, the roots of cassava plant must be peeled, washed and
grinded and afterward passed to cooking and finally to the saccharification tanks, a process that
is alike to the ones used for corn bioethanol. This plant has industrial indices similar to the ones
of corn, this being for one ton of cassava in nature, containing about 2 5 % of starch, 170 liters
of bioethanol can be produced. Taking into account what was previously mentioned and the
average productivity level in Brazil, about 18 tons per hectare are produced and 3060 liters of
bioethanol derive from this. There are no co-products form this process besides the vinasse.
Another plant containing starch is Wheat and it is used also when producing bioethanol
in some European countries among England and Germany. The industrial process for the
obtention of bioethanol is relatively similar to the one used for corn. The productivity is
typically 7.5 tons per hectares for agricultural productivity and 240 liters of bioethanol in
industrial productivity per ton of processed grains (LowCVP, 2004) leading to a production of
1800 liters per hectare. Around 320 kg per ton result as a coproduct from the harvest of the
grain, this being used as animal feed.
Sugar beet, being among the sugar producing crops like cane, is used to manufacture
bioethanol. Molasses, which is always available when producing sucrose, is used for the
production of bioethanol. The roots of this plant are tuberoses and contain important amounts
of sugar, the productivity of the crops is between 50 and 100 tons per hectare and sucrose
content of 18 % (RIRDC, 2008) and reaching 7500 liters of bioethanol per cultivated hectare.
The process begins with cleaning and fractionation into small pieces of beet, subsequently
taken to diffusers to be cleaned with hot water in order for them to release the sugar, this liquid
that results from the process contains 16 % soluble solids extracted from the beet that is
processed in the same way as cane juice, sugar or bioethanol. A ton of the plant can produce 86
liters of bioethanol and 51 kg of fibrous cake used as animal feed. Even though it has high
productivity, this process is dependent on external energy for its production.
Even though the significance of the production of bioethanol with Sorghum bicolor, it is
proposed potentially as a source of raw material for this process. It is being seen as a potential
material to be added to the production of bioethanol from sugar cane. In this case, the harvesting
period would be extended. The steams of this plant can be processed to produces a juice that
contains a lower sucrose content than cane juice that could undergo a similar process to produce
bioethanol.
The industrial productivity of this plant would be 40 liters of bioethanol per ton (Reddy,
et al., 2005) and agricultural productivity of 50 tons per hectare. The agro-industrial
productivity is 2000 liters of bioethanol per hectare. Nonetheless, the production of bioethanol
from sorghum is still being studied as it has some difficulties before it is adopted effectively as
the results obtained in Sao Paulo were not promising.
When selecting a crop for the production of bioethanol the consideration of budgets of
efficiency is essential, in a broad sense. The prioritization of crops that require less land, water
and external impute of agrochemicals, among others, is necessary. Additionally, and equally
important, it must be considered the economic viability, the economic efficiency is key.
Between 60 % and 70 % of the total price of production of bioethanol comes from the raw
materials used thus, the search of low-cost crops is fundamental. In equal importance stands the

39
existence of coproducts and byproducts in order to associate the availability of biofuels with
other economic value sources.
An additional issue in the selection of biomass is the energy balance of the crop, this
being the relationship with the energy produced and the demanded indirect or direct energy for
its production. Highly productive and low energy consumption crops are more viable.
Previous agronomic studies must be done before the selection of some unconventional
crop for the production of bioethanol. However, a sustainable and consistent diversification of
the supply of raw materials for the production of bioethanol might take place.
In contrast, there are some cases like the one for Colombia, whereas the country signed
the Paris Agreement, committing to a reduction of the carbon dioxide emissions by 20 % by
2030, and bioethanol contributes to this goal since the mixture of it with gasoline makes it more
energy efficient and friendlier with the environment. A mixture containing 10 % bioethanol
increases 3 octanes to regular gasoline and 2 for the premium one, allowing more efficient
technologies for vehicles in the country and a reduction in prices of fuel.

2.2. Methane Production from co-digestion in AnSBBR

In the search for less polluting fuels and in this case, a sustainable feedstock for bio
ethylene production through OCM, methane obtained from anaerobic digestion using wastes
from industrial and/or domestic sources have been studied. Besides vinasse, which was already
mentioned before, cheese whey, a major co-product from the dairy industry is mentioned by
Siquiera, et al. (2018) due to the impact in the depletion of oxygen if and when discharged into
waterbodies because of its organic load. Thanks to its nutritional value, whey is used as raw
material for animal and human consumption.
On the other hand, an average of 9 to15 L of vinasse is co-produced for each liter of
ethanol produced (CGEE, 2009), and vinasse production and characteristics can vary widely
depending on the raw material and the production process. This waste is acidic (pH 4.46 – 4.8)
and presents high organic matter content such as carbohydrates, proteins, and vitamins (U.S.
Department of Agriculture, 2008).
After Vinasse is produced as a co-product (or waste) in the fermentation subprocess of
Bio-ethanol production, is usually sent for soil disposal due to its high content of nutrients and
minerals that are essential for plant growth. Although there are some benefits in this technique,
such as reduction in the use of fresh water, mineral fertilizers, and the obvious economic
advantage, the direct application of stillage on the soil is problematic, since its low pH and high
sulfate and organic matter concentrations compromise soil structure and the surrounding water
bodies, in addition to reducing crop productivity
For instance, a middle size sugar and ethanol facility in Brazil produces and disposes of
around 2.000.000 m3 of vinasse during the harvest period. As only 8 out of 165 distilleries in
the of São Paulo have implemented alternative processes for the vinasse treatment, such as
anaerobic digestion, hence, irrigation of land has become a problem due to the expansion of the
land been spread with vinasse and affecting the sugar cane production itself.
Such kind of obstacles for Vinasse disposal creates a need for new waste management of
this bio-ethanol production coproduct. It has been proved that anaerobic digestion of such
polluted wastewaters can be used for biogas production from the organic matter present in the
effluent.
Considering these processes, the anaerobic digestion of vinasse presents advantages such
as low biological sludge production, lower need for nutrients, and production of methane, which
can be used as a power source. Nevertheless, the existence of organic compounds, like phenols,
may create instability in processes reducing the methane production efficiency, lowering the
acceptance of this alternative.
40
 This obstacle may be overcome by a co-digestion process involving a secondary
substrate, the mentioned cheese whey. This alternative is considered new as only appeared in
the literature in the latest ’80s. Yet, many studies have been performed form the 2000’s to find
the correct features to conduct this technique maximizing the digestion speed and efficiency,
and it was found that co-digestion process is able to handle the dilution of toxic substances by
using the micro-organism synergetic effects while increasing the methane yield and the
biodegradable matter content in the bioreactor.
Although anaerobic sequencing batch and fed-batch biofilm reactors (AnSBBR) have
been used many times previously for bioenergy generation, few studies have been conducted
for methane conversion from the vinasse resulting from bioethanol production. Nevertheless, it
was found by Almeida, et al. (2017) that an AnSBBR working with vinasse, performed better
than other batch reactors even when working with other types of wastes.
Almeida, et al. (2017) and G. Lovato, et al. (2018) performed a new process where the
co-digestion of vinasse and cheese whey were assessed within an AnSBBR operating in
sequence batch with the immobilized biomass and liquid phase recirculation for biomethane
production.
This pathway using this type of bioreactor represents a new option for medium agro-
industrial waste producers that might find a new alternative to lead with low profitable co-
products or those presenting restrictions for disposing of them.
The substrates used for co-digestion were industrial vinasse-based wastewater from a
sugar and alcohol plant located in the state of São Paulo, Brazil, and a cheese whey-based
wastewater (Lovato, et al., 2018).
The experiment was performed to illustrate the behavior of the AnSBBR laboratory
reactor taken to an industrial scale using date from a biorefinery in Brazil. The scale-up was
performed considering a vinasse production of 1.961.648 m3, volume fed into the industrial
reactor with a vinasse chemical oxygen demand of 25 g L-1 and a whey chemical oxygen
demand of 80 g L-1 and keeping the ratio of feeding for each co-substrate.
A mass balance for industrial level AnSBBR inflows and outflows were calculated
considering laboratory parameters such as organic load removed, influent concentration,
volume fed per day, number of cycles and length. Dilution rates for vinasse and whey at
industrial scale were also determined by the laboratory data.
A scheme of the system that was used in the laboratory phase to produce methane by
digesting vinasse and whey anaerobically is shown in Fig. 2.7.
The results from the experiments conducted by G. Lovato, et al. (2018), proved the
necessity of a more biodegradable co-substrate as it was hard to produce biogas from anaerobic
digestion using only vinasse. The same results were found for hydrogen production when using
an AnSBBR with vinasse as the only wastewater feedstock.
Now according to G. Lovato, et al. (2017) “the choice between a reactor operating in
continuous or discontinuous mode can be crucial for the efficiency and effectiveness of the
process. Continuous reactors are characterized by higher sludge retention time, high efficiency
and volumetric capacity process treatment but have long periods of start-up and are unsuitable
for wastewaters with low organic load.” Nonetheless, batch reactors are more flexible, are safer,
have lower installation costs, and increased control over the quality of the effluent can be
employed.

41
Fig. 2.7. Scheme of the AnSBBR with recirculation. 1. Reactor with immobilized biomass; 2.
Side reservoir; 3. Recycle pump; 4. Flowmeter; 5. Feed pump; 6. Wastewater reservoir; 7.
Discharge valves for pumping; 8. Discharge pump; 9. Effluent outlet; 10. Biogas outlet; 11.
Automation system. [G. Lovato, et al. 2018]

From the studies performed, it was concluded that a reactor volume equal to 67800 m3
would be required to accomplish the co-digestion of vinasse and cheese whey under the
proposed treated volumes. Hence, it was proposed a parallel configuration comprising four
AnSBBRs for industrial operation, each one of them with a capacity of 16950 m3. The benefits
from this arrangement is that allows the continuous production of biomethane while feeding,
reaction and discharge can be performed in one of the other reactors, this way intensifying the
productivity.

2.3. Oxidative Coupling of Methane (OCM)

The Oxidative Coupling of Methane is a process conducted at 700 ≈ 950⁰ and at up to 32
bar while purification and separation stages. One of the many challenges this process presents
is the one of conduct the reaction in a safe manner due to the big amount of heat is generated
(Mleczko & Pannek, 1996). Until now, according to Zaman (1999), this safety issue has been
one of the main reasons why OCM has not been deployed at Industrial level followed by
handling gasses close to the flammability area and auto-ignition temperatures. A HAZOP
analysis was performed by Stünkel, et al. (2012) to identify potential hazards while operating a
mini-plant and to come with a safety guideline for future replications. It was found that the most
important measures are the physical separation from adjacent laboratories “by declaring the
mini-plant as an “Ex-Zone 2“ according to ATEX classification”, installation of flame detection
systems, steady and constant ventilation in the process area and walls equipped with pressure
relief hatches. Valuations for severity degree and possible consequences were performed using
a simulation tool (ProNuSS), afterward, safety measures as relevant laze of controls and
shutdown procedures were implemented under the idea of redundancy at different levels.
Therefore, all OCM reactors are equipped with flame traps to avoid potential ignition spreads.
Other safety measures such as reduction of temperature at the outlet of the bed reactor to reduce
the hazard of ignition, dilution of gasses with high methane content using inert gas and staged

42
oxygen dosing procedures were all implemented to decrease the likelihood of explosion in the
Mini-Plant.
In the OCM reactor, a complete oxygen conversion is needed in order to obtain a safe and
successful purification and separation processes. Oxygen content is monitored at the reactor
outlets in order to ensure a rapid response if necessary. OCM reactors can be made from
explosion pressure resistant steel or totally cased in quartz material, both of them ensuring no
further damage to the plant in case of the explosion. Another safety measure is the implemented
procedures to cut off gas supply whenever abnormal temperatures or pressures arise.
In Stünkel, et al. (2012) study, three different reactors were analyzed to understand their
potential in the OCM process. A fixed bed one, fluidized bed one and a membrane reactor were
considered. All of them have different feeding procedures. But not only feeding is different
between them, safety features and operating procedures are also different. That is why some
operational parameters were tried to comprehend, such as temperature, pressure, inert gas,
catalyst and internal structure along with the reactors.
In the end, the performance of each reactor was considered within the OCM process.
Fluidized bed reactor: Due to its rapid fluidization area, isothermally operation can be
achieved even while handling the highly exothermic OCM reaction. When safety and operation
are considered, FBR is highly stable and efficient.
Fixed bed reactor: This is the most common type of reactor used for catalytic gas phase
reaction in the Industry. Although performance and feeding policy is almost the same as the
fluidized one, a hot spot formation can be clearly observed, which a big concern for the OCM
reactor operation. The hot spot formation can heavily reduce C2 production. Hot spots also
depend on the method catalyst was prepared, operational conditions, and the number of inert
gas diluents among others. These variables can also affect the catalyst thermal stability in
different ways along with the three studied reactors.
Membrane reactor: Are usually the most used for OCM process, and this has led to several
types of membranes have been tested, as porous inert to dense catalytic ones. C2 selectivity is
achieved in a membrane reactor thanks to the fine dosing of oxygen throughout the catalytic
bed. This oxygen feed can be done even from the air, by supplying it through a dense oxygen
permeable membrane.
Nevertheless, the permeability in such membranes is not enough to obtain high amounts
of methane while increasing C2 yield. For the OCM mini-plant, the Membrane reactor was
finally selected due to the reduction of hot spot formation compared with the fixed bed reactor
even when the thermal performances are not as high as the one observed at the fluidized bed
reactor, but, on the other hand, the C2 selectivity and yield are higher than in the last mentioned
reactor type. Higher yield and C2 selectivity were considered of greater importance than some
level of hot spot formation, as more selective performance and yield would reduce the fixed
and operating costs in the purification and separation following subprocess.
Experiments results conducted on a porous membrane reactor showed 4-6 % higher C2
yield than in the fixed bed reactor and less CO2 production than in the fluidized bed one.
For the following subprocess, (see Fig. 2.8) a separation unit is needed to be followed by
a carbon dioxide capture unit and finally, the separation equips for the intended products. As
CO2 removal and separation of the products require a large amount of energy and great
investments, Stünkel, et al. (2012) performed a benchmark OCM process for each section
aiming to find the best alternative to improve the process efficiency and optimize the energy
performance. The CO2 removal unit is probably the most important one as carbon dioxide is
the main co-product and the first one to be separated. Hence, an amine absorption process was
constructed at the Berlin Institute of Technology and a polymer separation system was also
investigated as an alternative process.

43
 Chemical absorption is a well-known technology and many different types of amines have
been developed for almost 90 years. For the benchmark absorption process conducted, 30 wt%
monoethanolamine (MEA) was used as an absorbent. The process was designed according to
results obtained in a simulation model on ASPEN Plus®. The kinetics for reactions between
MEA and CO2 were adopted from Hikita, et al. (1977) and applied using the Aspen Plus®
MEA-REA packed column. The mass transfer phenomena were simulated using the built-in
RateSep approach in the packed column. The results from the simulations and the experimental
results showed a good correlation and were validated for ambient and flue gas conditions.
Therefore, the model was applied for predicting the performance of the OCM downstream
process.
There was another amine investigated under the study, N-methyl diethanolamine
(MDEA). This amine presents some advantages in the regeneration step and requires less
energy for this. Experimental validation led to the conclusion that the use of MDEA combined
with 3wt% piperazine as an activator, reduced the energy demand compared with the MEA
results. Such absorption profile was compared with the forecasted data obtained from Aspen
Plus simulation finding a good correlation.

Fig. 2.8. Mini-Plant for OCM process. Absorption CO2 column, membrane unit with
absorption column and membrane reactor. [Stünkel, et al. 2012]

All mentioned experiments were conducted by Stünkel, et al. (2012) in a mini-plant (Fig.
2.8) containing more than 150 sensors and operated by a Siemens process control system PCS-
7. The design pressure for the absorption column is 40 bar and all the experiments were
conducted at the 5-32 bar. Liquid and gas sampling points were constructed in addition to the
two sample points at the inlet and outlet streams of the column. A desorption column was set
with a partial condenser and a reboiler, in order to regenerate the absorbent. This Absorption-
regeneration process was run continuously.
During the study, the effect of the solvent regeneration and the rate of mass flow were
investigated and adjusted to find the optimal mass flow to reach the maximum efficiency at the
reboiler heat duty. After the experiments, 90 % of CO2 was removed and captured showing how
mass flow rate and reboiler duty are key factors. The reboiler power was held constant while
44
the circulation flow rate was varied, afterward the reboiler power was reduced and then the
solvent flow was changed until finally find the minimum energy demand.
To find a commercial and sustainable OCM method, higher energy efficiency had to be
found. Hence, an alternative process for CO2 removal was investigated under the same study as
membrane separation is the most promising for the downstream process. Membranes have some
features that make them interesting when the goal is to reduce energy consumption, as they are
easy in operation, the modular installation allows easy scale-up in capacity and needs only a
short start-up and shut-down time. Dense membranes used in selective gas separation usually
come made from a cellulose base or a polymeric one. The last one is the most preferred for CO2
separation. Aspen Custom Modeler® was used for studying the applicability and efficiency of
such a membrane in the OCM process. According to the simulation results, the polyimide
matricide material has the best results for carbon dioxide separation. Afterward, a membrane
module with a GKSS flat sheet envelope type was installed to validate model results and also
to assess the technical feasibility of this unit.
After installing the polyimide matricide membrane module, the carbon dioxide
concentration was dropped from 25 % vol. to 17 % vol. thanks to a 0.5 m2 membrane unit.
Then, to achieve the desired energy reduction activated MDEA using piperazine was used
giving form to a hybrid process. This hybrid process configuration showed an overall specific
energy demand per captured kilogram of CO2 equal to 2.74 MJ kg-1 CO2.

Fig. 2.9. Concentration profiles for CO2 absorption [Stünkel, et al. 2012].

The results of this study proved that the use of a membrane and the piperazine activated
MDEA can reduce radically the energy demand for CO2 removal sub-process within OCM.
Another benefit found was a much higher removal rate than the usually obtained when only 30
wt-% MEA solution is used as absorbent (Stünkel, et al., 2012).
In Fig. 2.9, can be observed how the 90 % carbon dioxide removal target is obtained after
3 m of column height saving 2 m from the standard method. The solvent flow rate was also
reduced by 20 % in this hybrid process if compared with 30 wt-% MEA method.
These results are translated into an energy efficient CO2 capture process for OCM,
meaning a 40 % energy reduction, 40 % in column height and more than 20 % in solvent flow
rate, due to the designed membrane-absorption hybrid process.

45
 3. LIFE CYCLE ASSESSMENT METHODOLOGY
It was mentioned before; Life Cycle Assessment is one of the most used tools when
measuring and comparing products and/or its production activities environmental impacts.
Some results from business as usual methodologies for ethylene production as MTO, CTO,
Steam cracking of mixed hydrocarbons, and even Biomass to Methanol way, have been already
discussed. However, although OCM using Bio-Methanol produced from Molasse, has been
proven to be an economically feasible alternative for industrial deployment, there are no LCA
results that allows comparing the real impact from this pathway for ethylene production in the
environment.
The LCA methodology can be summarized in four stages, Goal and Scope definition,
Inventory Analysis, Impact Assessment and Interpretation:
o Goal and Scope definition
✓ defining the product system
✓ decisive for interpretation and use of results
o Inventory analysis
✓ collecting in-and output data for all processes
o Impact assessment
✓ assessing environmental relevance
✓ comparison of incompatible
o Interpretation
✓ sensitivity analysis
✓ outcome interpreted in relation to the goal.

3.1. Goal Definition

This particular study has as objective, assess the environmental impact of the Vinasse
production in Brazil using Sugar cane as main Raw Material for the latter production of Bio-
ethylene via OCM process to deliver reliable data to further comparison of the whole process
shown in Fig. 3.1. This data will be of high importance for Brazilian project developers and for
future ethylene buyers around the world as a making decision tool.
Said this, the present study fits into the definition of attributional modeling as the intended
use is to understand the relevant physical flows and no flow is to be changed in response to a
substitution of material. However, in the future, the whole process itself including the
production of methane by AnSBBR and the OCM to produce green ethylene is subject to be
analyzed to comparison with other pathways to obtain the chemically same ethylene or green
ethylene.

3.1.1. LCA System Boundaries

In Latin America, the agricultural activity is one of the most important economic basis,
specifically in Colombia and Brazil the growing of sugar cane is favored by the fact that the
climate conditions are ideal throughout the whole year. This region is the one that provided the
conditions to produce sugar cane during the whole year, allowing this region to specialize in its
production, and as a result, being the most productive area for harvesting this type of plant.
In Brazil, since the 1970s the country experience rapid growth in sugarcane plantations
powered by the political willing to reduce the dependence on foreign oil under the ethanol
program. The use of land to produce biofuels or bioplastics, arises a social concern regarding
the competition for arable land in food production and an environmental one. Fortunately,
sugarcane crops areas are very distant from the Amazon rain forest, mainly in the south and
southwest part of the country. Nevertheless, there is around 7.8 million ha (2007) dedicated to
46
sugarcane crops in Brazil, representing only one third of the area used for soybeans and half of
the area used for corn. It is worth to notice, Brazil has 22% of the arable land in the world, but
only 19% has been used so far (De Andrade, et al., 2013).
Similar policies have been developed in Argentina and Colombia for sugarcane
harvesting. Colombia for instance produced approximately 456 million liters of bioethanol in
2017 and more bioenergy plants are under construction. In the case of this country, the program
of production has the goal to improve the quality of petrol gas by the mixing of 10% in the final
volume.
The costs attributed to the production of bioethanol from sugarcane in Colombia, are
calculated between 27 and 30 cents USD per liter of ethanol. On the other hand, the returns on
this product are over 20% which makes all the projects alike very attractive to the investors.
The main by-product of sugarcane is bagasse, the residue from sugar extraction after
milling. This bagasse is used for producing renewable electricity to power all the processes
involved in the facilities for ethanol production and the surplus is sold to the national power
grid. As mentioned by Morschbacker (2009), the energy balance of sugarcane is very positive
if it is considered the necessary fossil energy input for the entire ethanol process, divided by the
energy content in the biofuel plus the electricity generated from its bagasse. For Brazilian
sugarcane ethanol the energy balance is 1:9.
In the Brazilian case, considering the average values observed in about 60 plants in the
state of São Paulo, with the losses referred to a medium cane with 14% sucrose content
(Morschbacker, 2009). Based on these performance values, in the case of the exclusive use for
the production of bioethanol, with one ton of cane it is possible to obtain 86 liters of hydrated
bioethanol, while, those facilities which objective is a combined production of sugar and
ethanol can obtain 71 kg of sugar and 46 liters of hydrated bioethanol produced the molasses
(CGEE, 2009).
The production of vinasse in this project, represents only one part of the total new
proposed process for bio ethylene production to be deployed in Brazil, it is necessary to set the
boundaries for this first part of the production chain. The whole product system for Bio-ethylene
production and the system boundaries is shown in Fig. 3.1.
From Fig. 3.1 can be said, the agricultural activity is taken into account within the
boundaries, followed by the extraction of the sugarcane juice by a simplified process
considering the milling, and the juice clarification. Then the fermentation process using yeast
giving place to wine is considered, and finally the distillation process where ethanol is separated
from vinasse. It is worth to notice, that the dehydration of ethanol by using cyclohexane in an
extra purification column is considered within the boundaries for the studied system.
Storage and transport of products are beyond the boundaries as the intended new bio
ethylene production facility should be located in a near area to the biorefinery, leaving these
transport considerations for a future or likely LCA on the anaerobic co-digestion of vinasse and
whey cheese process to obtain bio methane.
As most of the data collected for the bioethanol process production industry in Brazil
correspond to values found in the literature between 2011 and 2016, the time boundary is
defined for this period and can be considered as still valid as there are no new manuals for
sugarcane production published or new improvements have been found since the harvesting
procedure change to mechanized cutting and transport was introduced.

47
 Fig. 3.1. System Boundaries

3.2. Scope
Scope definition requires clearly describing the function and functional unit, system
boundaries, methodology, and data requirements sufficiently to address the stated goal. As said
before, an attributional model is going to be performed for this study to calculate the
environmental load of Vinasse production from Sugar Cane in Brazil.
The time frame of the study only includes existing technologies and described
technologies in this project. Hence, the effect of new technologies will not be taken into
consideration. As can be seen in fig 3.1, this model will be based on a Cradle to Gate approach.
For vinasse production, Annex 1 shows a general scheme used at most common sugar
cane facilities for refined sugar and ethanol production.
Within the agricultural stage, transport considering new mechanized process was
considered. use of raw materials for sugar cane crops are also taken into account including land
use, water and fertilizers. The industrial phase accounting for the wine production, resulting in
the obtention of bagasse waste, heating and clarification steps required are within the scope as
they correspond to intermediate subprocess. Fermentation and distillation processes required to
obtain vinasse and purified bioethanol are the final steps considered for this LCA.
Vinasse as final product in this cradle to gate approach was the chosen final step as it was
not only the defined objective delivered by the thesis supervisor but also because of the
increasing researches regarding the use of vinasse for biogas production, and the option of keep
using it as fertilizer for sugarcane crops avoiding the use of inorganic chemicals.
The scope of this project is under a stand-alone type of LCA analyzing the current and
best available technology in Brazil for bioethanol and vinasse production from sugarcane. The
baseline scenario is the one described in the previous chapter, and it was subject to sensitivity
analysis for the methodology and also for the electricity. However, a comparison between the
baseline scenario and the included process for bioethanol production from sugarcane already
existing in simapro is conducted with the only objective of validate the accuracy of the
simulated scenario and its gathered inventory and established limitations and assumptions.

48
 The production of ethanol from conventional sources by ethylene hydration cannot be
compared directly with the production of bioethanol from sugarcane, mainly because there is
no coproduct such as vinasse resulting from it, which is the desired effluent for further bio
ethylene production in this work. In case a comparative analysis is desired, the whole
production of bio ethylene from vinasse going through the anaerobic co-digestion in AnSBBR
should be the pathway to compare versus the obtention of ethylene from all the available and
conventional sources discussed in chapter 1.
In the study made by Zhao, et al., (2018), LCAs comparing the production of ethylene by
most of the conventional sources with its obtention from the transformation of bioethanol into
ethylene through ethanol dehydration was conducted and it was found that this pathway is one
of the only three out of ten than can deliver negative CO2 emissions.

3.2.1. Functional Unit

A functional unit (FU) is a measure of the performance of the functional outputs of the
product system and its primary purpose is to provide a reference to which the inputs and outputs
are related. This reference is necessary to ensure comparability of LCA results. The definition
of a functional unit must hence include both the quantitative and the key qualitative aspects to
avoid subjectivity when subsequently defining an equivalence. Especially for complex
products, that may differ in a number of qualitative aspects (e.g. two cars of different levels of
comfort), is important that the equivalence of the “functional unit” is carefully defined to ensure
valid and defendable comparisons and even more so for comparative assertions disclosed to the
public.
For this study, the functional unit has been defined accordingly to Bio-ethanol production.
It was assumed an ethanol yield close to 90 % delivering a total concentration of 10 % in the
final broth after fermentation, meaning that for each ton of sugarcane processed, 85 L of
Bioethanol were obtained resulting in a vinasse volume of 765 L. Hence, a functional unit of 1
ton of sugarcane is considered.

3.3. Limitations and assumptions

Several assumptions had to me bade for this process and most of them are to be described
within the summary of each process presented in the life cycle inventory sub chapter to come.
One of the limitations was done regarding the emissions to the soil or waste generated after the
5th cycle of sugarcane harvesting. As the productivity decreases after each cycle (see Table 3.1),
the area is cleaned by the removal of roots and leaves. However, under the literature review
performed it was not possible to find the amount of mass collected in this activity, hence it was
disregarded.

Table 3.1. Typical cycle of sugarcane in Brazil (Macedo, et al., 2004)

Harvesting Sugarcane productivity (ton/ha)
1st cycle (seeding and planting) 113
2nd cycle 90
3rd cycle 78
4th cycle 71
5th cycle 67
Average 82.4

Considering the Table 3.1, a productivity of 80 ton per ha was assumed with 85 L of bio
ethanol per 1 ton of processed sugarcane as mentioned before for the functional unit definition.
The amount of bagasse recovered from the milling process was assumed as 260 kg according
to the information found in (Coordinacion BNDES y CGEE, 2008).
49
 The infrastructure in the industrial stage was not considered in this work leaving aside
distillation columns, reactors for fermentation and all grinders required for the milling
subprocess.
It was assumed the biorefinery will be self-powered by the production of electric and
thermal energy using the recovered bagasse as this is a common practice in most of these
facilities in Latin America.
The amount of water required for the milling process was calculated by the author, on
471 L considering a required sugar content in the juice about 150 – 200 g/L (Bai, et al., 2008).
Finally, in Brazil, the water requirement for the sugarcane crops, is mainly rainfed and
mechanical harvesting has been implemented reducing the environmental impact from previous
techniques which used to involve sugarcane burning performed by workers manually. It is also
assumed the Geographic position for the crops can deliver a high pluviometry index (above
1,200 mm) dropping the regular amount of water required.
It is for this reason that the World Bank and FAO have considered Brazilian ethanol to
be the only biofuel competitive with oil-based diesel that saves greenhouse gases
(Morschbacker, 2009).
During the sensitivity analysis for electricity, the required energy was taken from
(Coordinacion BNDES y CGEE, 2008) as displayed in Table 2.1. For more assumptions and
limitations regarding the baseline scenario, described subprocess should be read in detail in the
following sub-chapter.

3.4. Life cycle Inventory (LCI)

As a cause of global markets, many of this kind of processes are resembling or even
identical, like the extraction of oil in the Middle East or the manufacturing of steel in Asia.
Other processes show typical continental, national or even regional properties- such as the
generation of electricity, road transportation, cement manufacturing, and agricultural
production, respectively. Thus, a database providing high-quality data frequently used
commodities for life cycle inventories are helpful and requires, specifically if one wants to
apply LCA on a routine basis, for product development purposes. For this work, as bioethanol
production process from sugarcane in Brazil, and other starch sources are already contained in
simapro, the data collected was chosen carefully using only available values for current
production techniques in this country. Data used for this simulation was compared among
different sources such as scientific papers and country reports and manuals, finding correlation
between the reported yields, raw material consumption and employed technologies. Whenever
normalized data was not available under the defined functional unit, calculations were made
according to values reported and referenced.
The standard facility production is shown in Annex 2 using as a model, the layout for the
production flow process at the biggest bioethanol plant in Colombia (Incauca, 2019) and
matching with the described facilities reported for most of the sources regarding Brazilian
biorefineries.
Then, LCI is developed for every single sub-process and presented as follow.

3.4.1. Sugar Cane Production

For this subprocess, adequation land tasks will not be considered as it was assumed the
area is already set for the crops. After sugarcane is seeded, irrigation occurs immediately and
on a 2 weeks basis for the whole crop growing period (assumed to be 12 months). Irrigation
occurs according to the water balance schedule program that calculates the water needs of the
plantation based on the retention capacity of soil moisture, loss by evaporations transport and
rain contribution. Usually, in sugar production, most of the water demand for the crops is
50
supplied by the fertilization process using vinasse as potassium source, as in this case, vinasse
is our desired coproduct for bio-methane production, other water sources are considered as
rainwater and irrigation. The amount of water for irrigation during the period of growth of the
cane was assumed in 1.8 m3 as most of the water required is fed by rainwater in Brazil (CGEE,
2009).
Fertilizers such as Urea (Nitrogen source), Phosphorus, Calcium, and others are required
along with herbicides to avoid weed growth. Some activities performed during the 12-14
months the growing process takes, and that are undertaken in order to ensure the physical
integrity of the stem of the cane, the proper humidity of the land and to direct the water streams
during irrigation and during rain seasons, are not considered for this LCA as they are performed
manually and do not involve the use of any concerning chemical product. A general scheme for
the agricultural stage is displayed in Fig. 3.2.

Fertilizer

Land
Water Harvesting
Crops
Sugar Cane

Wagons Trucks Cropper Machines

Fig. 3.2. Sugar cane Production subprocess [Incauca, 2019]

For the harvesting task, special harvesting cropper machinery is used, and sugar cane is
deposited in 20-30cm long stems directly into the wagons for transportation within the internal
roads in the fields.
The cropped sugar cane is transported from the crop fields to the Refinery Warehouse.
From (Incauca, 2019) and (National Comitee for sustainable development of Sugarcane
(Spanish), 2015) it was calculated a total distance of 0.1 km for a harvesting machine to collect
1 ton of sugarcane; a total distance of 20 km to go inside of the field crops for collecting and
transporting 12 ton of sugarcane until the main road, resulting in 1.7 km/ton for the tractor; and
then, a distance of 40 km from the fields to the biorefinery (3.3 km/ton). The main concern
during this process is to reduce the time from cane is cut until is processed. to avoid the loss of
sucrose content, since from the burning or cutting of the cane a degradation process is initiated
that decreases the sucrose content, due to the action of the invertase enzyme that converts part
of the sucrose into glucose and fructose. The rate for loss of sucrose, with prior burning or
without burning, varies from 0.018 to 0.7% of cane weight per day. Amounts for fertilizer
elements were calculated for the functional unit using data available in (Romero, et al., 2009)
and (Pereira, et al., 2019).
For the land use, productivity of 80 ton/ha was assumed considering the values found in
CGEE (2009), leaving as a result an area of 125 m2 per harvested ton. The LCI for this
subprocess is presented in Table 3.2.
As the functional unit was defined as 1 ton of processed sugarcane, the land use was
calculated considering that 1 hectare is able to produce 80 tons of sugar cane. For water, it was
assumed that most of the required water is supply by rain, still, irrigation would be needed
during dry periods with a total consumption of 1.8 m3 ha-1 during the whole growth period of

51
sugarcane. For transportation and machinery, transport materials from the simapro database
were used keeping accordance with the functional unit.

Table 3.2. Sugar Cane Production LCI

PROCESS: Sugar cane Production
INFLOWS
Material data/info unit
Land Use 125 m2
Water 1.8 m3
K2O fertilizer 3.8 kg
Urea (Nitrogen) 1.6 kg
P2O5 fertilizer 1.0 kg
Sulfur 0.3 kg
Calcium 0.7 kg
Magnesium 0.4 kg
Wagons 0.1 Unit
Harvesting Machinery 0.1 km/ton
Tractors 1.7 km/ton
Transport to Refinery 3.3 km/ton
Energy data/info unit
Electricity MWhel/1year
Heat MJ/1year
OUTFLOWS
Products and Co-Products data/info unit
Sugar Cane 1 ton
Emissions1 data/info unit

The transport to the refinery was simulated using freight with 7.5 – 16 metric ton capacity
according to (National Comitee for sustainable development of Sugarcane (Spanish), 2015)
recommendations. Although it is well known that pesticides are used for this type of crops,
there is a gap in the data as an inventory for this particular material could not be found either in
the available literature regarding sugarcane production nor in similar LCA.

3.4.2. Sugar cane Juice Production

With almost not stocking time, sugar cane is taken to the millers usually distributed in
parallel assemblies of 6 millers each of them with 4 grinders that compress the cane to extract
the juice. The waste from a grinder goes to the next one to extract the maximum amount of
possible juice. From the last grinder, bagasse with low saccharose and moisture content is
obtained. Approximately 90 % of Bagasse is sent to the boiler house as fuel for Steam
generation in a co-firing process along with Coal. The remaining 10% is sold for paper
production. The juice is then sent for the Sulfidation to avoid pigmentation during following
processes and lime addition for alkalization to prevent saccharose reverse. The heater uses

1
Air emissions from machinery and transport vehicles are considered within the simapro software and were
included in the simulation even if not shown in this table.
52
steam to reach 65⁰C, the temperature at which process occurs. The simplified steps for wine
production can be seen in Fig. 3.3.

Water Coal

Baggase Sugar Cane Juice Lime

SO2
CaHPO4

Heater Clarified Juice

Steam
Miller Clarifier
Heated Sugar cane Juice

Electricity Sedimentary Mud

Recovered Juice
Low Pressure Steam

Heated Water

Sugar Cane Filtration Process

Mud Waste Paste

Electricity to the Market

Fig. 3.3. Sugar cane juice production subprocess [CGEE, 2009]

The energy required for this subprocess is all supplied from the electricity generation
plant and the steam for heating the juice is the low-pressure steam waste remaining. This is a
common practice in the main bioethanol facilities in Brazil and Colombia (Incauca, 2019) and
(Morschbacker, 2009). This capacity for energy auto supply will be considered during the LCA
simulation. Although the electricity generation is out of the boundaries, the electricity and heat
output will be considered as zero as even when coal for cofiring process is required, sugar cane
cogeneration accounts for 6 % of the power generation capacity in Brazil (De Andrade, et al.,
2013). Data for other materials as Sulphur dioxide and Lime were gathered from the LCA work
conducted by (Pereira, et al. (2019).

Table 3.3. Sugar cane juice production – LCI

PROCESS: Juice Production (Milling, heating, and clarification)
INFLOWS
Material data/info unit
Sugar cane 1000 kg
Water 451 L
Lime 9.2 kg
SO2 6.3 kg
Energy - -
Electricity - MWhe
Heat Necessary to reach 65⁰C MJ/1year
53
 OUTFLOWS
Products and Co-Products data/info U.M.*
Sugar Cane Juice 1121 kg
Bagasse (dry) 260 kg
Emissions data/info unit
Sedimentary mud 70 kg

3.4.3. Fermentation and Distillation Process

Fig. 3.4 (a) shows how the juice, rich in glucose (150 – 200 g/L) is sent to the reactors in
addition to the yeast at a concentration lower than 40g/L, for the glycolysis metabolic process,
where under anaerobic conditions the glucose is transformed into pyruvate within the yeast cell
membrane to produce pyruvate, which later is converted into ethanol releasing CO2. The
theoretic selectivity from pyruvate to ethanol is 51 % and 49 % for CO2 (Bai, et al., 2008). For
own mass balance calculation, a Vinasse density of 1.29 g/mL was selected (U.S. Department
of Agriculture, 2013) and an initial yeast concentration of 40 g/L was assumed (Bai, et al.,
2008). The glycerol obtained from the EMP pathway, corresponding to almost 1% (w/v) is the
only one other co-product considered for this work. By mass balance and considering an ethanol
density of 0.789 g/cm3, the final products and coproducts were calculated to be displayed in
Table 3.4. Carbon dioxide is retrieved from the fermentation process, leaving the molasse after
yeast is recovered, free to be sent to the distillation columns. As can be seen in Fig. 3.4(a).

Fig. 3.4. (a) Fermentation process, (b) Ethanol distillation process

54
 The wine, the resulting product from the fermentation process containing vinasse and
ethanol is sent to distillation columns after yeast is recovered either by a settling tank or by
centrifugation. The recovered yeast, ethanol and glycerol were considered as avoided products
from Vinasse production, as this yeast is processed in order to be reused and glycerol can be
sold to other industries. Meanwhile, CO2 and water are considered as emissions, mainly because
no carbon capture and storage mechanism are mentioned in the literature regarding bioethanol
production facilities.
Fig. 3.4 (b) shows the distillation process in a summarized way, as this procedure might
involve usually 3 distillation columns. From the first one, vinasse is recovered for later
evaporation if needed.
Hydrated ethanol is sent to dehydration column where hexane is added in amounts
calculated by Pereira, et al., (2019), to form an azeotropic mixture with present water with a
lower boiling point than anhydrous ethanol. This way bioethanol is obtained from the bottom
of the column and the azeotropic mixture can be later on condensed and cyclohexane recovered.
This last process for cyclohexane recovery was not considered within the boundaries for
assessment.
The amount of vinasse obtained was calculated according to Morschbacker, (2009) and
De Andrade, Morita, Cassineli, Morschbacker, & Do Carmo, (2013) where they mentioned
average productivity of 85 L of ethanol per each ton of sugarcane processed. It was then
assumed a wine composition of 10 % ethanol and 90 % vinasse (Bai, et al., 2008) although the
ratio can be different upon the biorefinery studied with values up to 13 % for ethanol
composition (CGEE, 2009).

Table 3.4. Fermentation and distillation processes - LCI

PROCESS: Fermentation and Distillation
INFLOWS
Material data/info unit
Sugar Cane Juice 1121 kg
Yeast 30.6 kg
Cyclohexane 0.070 kg
OUTFLOWS
Products and Co-Products data/info unit
Vinasse 765 L
Recovered Yeast 122.4 kg
Ethanol 99.7 ° GL 65.73 kg
Glycerol 1.07 kg
Emissions data/info unit
Water 0.26 kg
CO2 67 kg

After defining the LCI, the Life Cycle Impact Assessment (LCIA) was modeled using the
software simapro 8.52v. The impacts on areas of protection such as human health, ecosystem
quality, climate change, and natural resources were calculated using Impact 2002+; an endpoint
method included within the software package. Each area of concern is evaluated through a
variety of environmental impact categories, for which an indicator result is selected and
calculated. The summarizing of such results provides information about the environmental
issues associated with the inputs and outputs of the system. This calculation is known as
55
Characterization within the LCIA. The impact categories assessed for the characterization of
this work were:
o Carcinogens
o Non-carcinogens
o Respiratory inorganics
o Ionizing radiation
o Ozone layer depletion
o Respiratory organics
o Aquatic Ecotoxicity
o Terrestrial ecotoxicity
o Terrestrial acidification/nutrient enrichment
o Land occupation
o Aquatic acidification
o Aquatic eutrophication
o Global warming
o Non-renewable energy
o Mineral extraction

56
 4. LCA RESULTS AND DISCUSSION
The LCI gathered was used for the simulation in Simapro in accordance with the defined
functional unit of 1-ton sugarcane processed. In Annex 3 the data entry for 1 metric ton of
sugarcane production is displayed. Annex 4 shows Simapro data entry for the production of the
clarified juice previous to the fermentation and distillation process. Annex 5 displays the entry
for Vinasse and Bioethanol production. Following results are presented for all vinasse
production stages considering a cradle to gate approach since the final use of bioethanol is not
considered and vinasse use is to be analyzed in accordance to the proposed new technological
pathway for bio ethylene production.

4.1. Life cycle data and interpretation

Interpretation of life cycle is done in relation to the goal and scope defined. Findings will
be qualified and evaluated for every single process. Then, hotspots are summarized to identify
significant issues.
The main units used for LCA interpretation are as follow (Humbert, et al., 2012):
For the midpoint level:
o kg substance eq. Expresses the amount of a reference substance equalizing the
impact of the analyzed pollutant under the midpoint category.
For damage level:
o DALY. Meaning the “Disability-Adjusted Life Years” and it is used to illustrate
s disease severity for carcinogenic and non- carcinogenic effects. For instance,
a substance with a human health score equals to 5 DALYs represents the loss of
five years of life compared with the overall population.
o PDF m2 y. Is the “Potentially Disappeared Fraction of species over a certain
amount of m2 during a certain amount of year” and it is used to measure
ecosystem impacts.
o MJ. Mega Joules expressing the amount of energy required to extract a resource
or extracted from it.
For normalized damage level:
o Points. These are equal to person-year and represents the average impact in a
determined category by one person during one year in Europe. Or, in the case of
human health, it represents the average impact on a person for one year. For
instance, an impact of 3 points in resources, means the average impact caused
by 3 persons for one year.
After running the simulation in simapro, the network obtained for the whole process
under study, reflects the importance of considering the bioethanol as an avoided product as
deliver a positive impact on the pretend scenario (see Fig. 4.1). The use of bagasse for power
generation is also seen as a positive impact while the process of harvesting the sugarcane crops
presents the higher negative impact just as the use of yeast for the fermentation of the sugarcane
juice into ethanol.

57
Fig. 4.1. Simapro Network for Vinasse Production from sugarcane
 4.1.1. LCA for sugarcane production
As can be seen in Fig. 4.2, in the agricultural and harvesting phase, the main relevant
items in terms of environmental impact for most of the categories is the use of fertilizers such
as potassium and phosphorus.

100%
90%
80%
70%
60%
50%
40%
30%
20%
10%
0%

Sugarcane crops Transport, freight, lorry 7.5-16 metric ton

Potassium fertiliser, as K2O Liquid urea-ammonium nitrate solution
Phosphorus, white, liquid Sulfur dioxide, liquid
Calcium ammonium nitrate Magnesium sulfate
Tap water
Fig. 4.2. Impact assessment characterization per impact category

Regarding the GHG, Table 4.1 shows how the main contributor in global warming is the
use of fertilizers for the crops, due to its manufacture and use. Data presented in Table 4.1 are
referred to as the functional unit (1000 kg sugarcane processed).
For land occupation, the sugarcane crops itself is the activity with the largest share even
when it was considered a high yield of 80-ton ha-1.

Table 4.1. Life cycle data for GHG in Sugarcane production stage
Global warming Unit (kg CO2eq)/1-ton sugarcane
Sugarcane Crops 0.00
Transport, freight, lorry 7.5-16 metric ton 1.09
Potassium fertilizer, as K2O 6.18
Liquid urea-ammonium nitrate solution 1.19
Phosphorus, white, liquid 12.11
Sulfur dioxide, liquid 0.11
Calcium ammonium nitrate 0.81
Magnesium sulfate 0.18
Tap water 1.17
TOTAL 22.82

Here it is important to notice that the carbon dioxide capture effect from sugarcane crops
is not considered under this study, yet many authors have referred to it as an additional positive
impact in the producing of bioethanol from renewable feedstocks (Morschbacker, 2009).
 Fig. 4.3 shows the weighting results for 1 ton of sugarcane produced, where a land
occupation has the greater impact in the production of sugarcane followed by respiratory
inorganics due to the use of Phosphorus pentoxide as fertilizer in a ratio of 1 kg per sugarcane
ton produced (Romero, et al., 2009).

10
9
8
7
6
mPt

5
4
3
2
1
0

Sugarcane crops Transport, freight, lorry 7.5-16 metric ton

Potassium fertiliser, as K2O Liquid urea-ammonium nitrate solution
Phosphorus, white, liquid Sulfur dioxide, liquid
Calcium ammonium nitrate Magnesium sulfate
Tap water
Fig. 4.3. Impact assessment weighting per impact category

From Table 4.2, can be seen how the higher impact received from this activity is on the
ecosystem quality, triggered by the sugar crops production as can be seen in Fig. 4.3. This
combined with the analysis performed on Fig. 4.2. reflects the large impact of the land use. It
can be considered as a hot spot and must be interpreted as the total of species might potentially
disappear on one square meter during one year according with the interpretations given by
Humbert, et al., (2012).

Table 4.2. Damage assessment for sugarcane production

Damage category Unit Total
Human health DALY 3.84E-05
Ecosystem quality PDF*m2*yr 138.08284
Climate change kg CO2 eq 22.82406
Resources MJ primary 350.8556

For the process of Sugarcane production, Fig. 4.4 shows the impact of the crops in the
ecosystem quality, with more than 80 % of the share in this area of concern. It can also be
observed the impact of fertilizers such as phosphorus and potassium affecting human health,
climate change and resources.

60
 100%

80%

60%

40%

20%

0%
Human health Ecosystem quality Climate change Resources
Sugarcane crops Transport, freight, lorry 7.5-16 metric ton
Potassium fertiliser, as K2O Liquid urea-ammonium nitrate solution
Phosphorus, white, liquid Sulfur dioxide, liquid
Calcium ammonium nitrate Magnesium sulfate
Tap water
Fig. 4.4. Damage assessment in areas of concern

Considering the impact in the land occupation, results for this impact category are
presented in Table 4.3 showing how the use of land for the crops itself is the main contributor.

Table 4.3. Life cycle data for land use in Sugarcane production stage
Land occupation m2org.arable
Sugarcane crops 110.09174
Transport, freight, lorry 7.5-16 metric ton 0.039108315
Potassium fertilizer, as K2O 5.7771429
Liquid urea-ammonium nitrate solution 0
Phosphorus, white, liquid 0.44628794
Sulfur dioxide, liquid 0.002633546
Calcium ammonium nitrate 0
Magnesium sulfate 0.003046232
Tap water 0.014784917
TOTAL 116.37475

The following material affecting the land occupation is the Potassium Oxide with only 5
% of the total contribution. The use of the remaining raw materials and equipment have almost
no impact in the land use mid-point category.
The impact in the human health area is also worth it for a deeper review as the use of
fertilizers show an important impact in the respiratory inorganics category displayed in Fig. 4.3.
Such results are displayed in Table 4.4.

61
Table 4.4. Life cycle data for human health in Sugarcane production stage
Impact category Carcinogens Non-carcinogens Respiratory Respiratory
(kg C2H3Cl (kg C2H3Cl eq) inorganics (kg organics (kg
eq) PM2.5 eq) C2H4 eq)
Sugarcane crops 0.0000 0.0000 0.0000 0.0000
Transport, freight 0.0085 0.0190 0.0011 0.0005
Potassium fertilizer, 0.3075 1.5601 0.0103 0.0024
as K2O
Liquid urea- 0.0000 0.0003 0.0006 0.0001
ammonium nitrate
solution
Phosphorus, white, 0.2021 0.1001 0.0285 0.0018
liquid
Sulfur dioxide, 0.0017 0.0024 0.0013 0.0001
liquid
Calcium ammonium 0.0000 0.0002 0.0005 0.0000
nitrate
Magnesium sulfate 0.0029 0.0016 0.0004 0.0000
Tap water 0.0599 0.0565 0.0028 0.0003
TOTAL 0.5826 1.7402 0.0455 0.0051

4.1.2. LCA for clarified sugarcane juice production

As mentioned before, this process encompasses three subprocess in one, Milling, Heating
and Clarification. Due to the fact, these biorefineries are power self-sufficient in Brazil and
other Latin American countries, the energy required for electricity and heating was not
considered within the boundaries.
Fig. 4.5 shows the midpoint categories results from the LCA modeling. Starting from this
graph, it can be noticed a negative impact (positive for the environment) from the avoided
bagasse production as it is used for power generation. It can also be noticed, how for most of
the impact categories, the carried load of the sugarcane crops is one of the main contributors.
This can also be seen in the characterized results displayed in Fig. 4.5. It must be noticed that
LCA results presented for this subchapter section (sugarcane juice production) are displayed
for the production of 1121 kg of clarified sugarcane juice, according to the normalized data for
the baseline scenario. Having this in mind, damage assessment results for this process are
presented in Table 4.5.

Table 4.5. Damage assessment for sugarcane juice production

Damage category Unit Total
Human health DALY -1.13E-04
Ecosystem quality PDF*m2*yr 117.3604
Climate change kg CO2 eq 27.901733
Resources MJ primary 506.82

In Fig. 4.5 can also be observed how the use of sulfur dioxide in the clarification process
has a high impact percentage in several impact categories, especially in the aquatic acidification
category. However, its true impact is discussed later on.

62
 100%
80%
60%
40%
20%
0%
-20%
-40%
-60%
-80%
-100%

Sugar cane Juice Sugarcane crops

Tap water Lime, hydrated
Sulfur dioxide Bagasse, from sugarcane {BR}
Fig. 4.5. Impact assessment characterization per impact category

It can be seen from Fig. 4.6, how the mPt for sugarcane crops under the land occupation
category are 9.3 representing the higher impact of all. Here, the bagasse as an avoided product
and its use for power generation under the Brazilian energy grid is accounted, delivering a
negative value under some human health mid points categories.

8
3
-2
mPt

-7
-12
-17
-22

Sugar cane Juice Sugarcane crops Tap water

Lime, hydrated Sulfur dioxide Bagasse, from sugarcane {BR}

Fig. 4.6. Impact assessment weighting per impact category

Finally, Fig. 4.7 presents the damage assessment per area of concern. From this, the main
relevant points are the benefit (negative impact) in human health basically gained from the use
of sugarcane bagasse avoiding the impact caused mostly by non-carcinogens and in a lower
share carcinogens substances (See Fig. 4.5).

63
 100%
80%
60%
40%
20%
0%
-20%
-40%
-60%
-80%
Human health Ecosystem quality Climate change Resources
Sugar cane Juice Sugarcane crops Tap water
Lime, hydrated Sulfur dioxide Bagasse, from sugarcane {BR}

Fig. 4.7. Damage assessment in areas of concern

Previously, sulfur dioxide use was seen as an important contributor in terms of percentile
points, but from Fig. 4.6 can be seen that its only relevant impact is under the respiratory
inorganics category, affecting mainly the human health area of concern and then the resources
one, but behind the impact delivered by harvesting sugarcane crops.
In Table 4.6 the benefit from the use of bagasse can be seen easily, and its benefit is clear
for the non-carcinogens category avoiding the emission of 49 kg of chloroethene (vinyl
chlorine).

Table 4.6. Life cycle data for human health in Sugarcane juice production stage
Impact category Carcinogens Non-carcinogens Respiratory Respiratory
(kg C2H3Cl eq) (kg C2H3Cl eq) inorganics (kg organics (kg C2H4
PM2.5 eq) eq)
Sugarcane crops 0.5826 1.7402 0.0455 0.0051
Tap water 0.0150 0.0141 0.0007 0.0001
Lime, hydrated 0.0292 0.0183 0.0025 0.0010
Sulfur dioxide 0.0674 0.0700 0.0292 0.0016
Bagasse, from
sugarcane {BR} -7.7649 -51.0136 -0.0144 -0.0047
Total -7.0707 -49.1709 0.0635 0.0031

Regarding the GHG emissions and land use, Table 4.7 is presented to display the main
contributors to these categories. From both tables can be concluded that sugarcane is the
material causing the larger impact as it was previously seen in Fig. 4.6. Compared with the
effect of sugarcane production in land use, other materials are practically zero. In the global
warming category, hydrated lime and Sulphur dioxide also have some effect in lower
proportions.

64
Table 4.7. Life cycle data for GHG and land occupation in Sugarcane juice production stage
Impact category Global warming kg CO2 eq Land use m2org.arable
Sugarcane crops 22.82 116.375
Tap water 0.29 0.004
Lime, hydrated 8.61 0.019
Sulfur dioxide 2.97 0.052
Bagasse, from sugarcane {BR} -6.79 -6.346
Total 27.90 110.104

4.1.3. LCA for vinasse production

The final LCA result in terms of midpoint categories can be observed in Fig. 4.8, where
the environmental load from all previous agricultural and biorefineries processes are
summarized under the flow for Sugarcane juice. As in previous LCA results, the data calculated
and presented in the following graphs are referred to the functional unit, in this case to produce
987 kg of vinasse, considering all data input was normalized to the established functional unit.

80%
60%
40%
20%
0%
-20%
-40%
-60%
-80%
-100%

Sugar cane Juice Fodder yeast

Cyclohexane Ethanol, without water, in 99.7% solution state
Glycerine

Fig. 4.8. Impact assessment characterization per impact category

As can be seen, the negative impacts are overlapping the positive ones due to the
assumptions and the way this modeling was conducted. As Bioethanol is considered an avoided
product, all the environmental load usually reported as positive, is observed here as a negative,
meaning savings in all the impact categories since it is understood as this bio ethanol is no
longer required to be produced in another similar facility. Table 4.8 shows the total value of the
four areas of concern. For a better understanding, these values are presented referred to the
functional unit. For instance, processing 1 ton of sugarcane to produce 987 kg of vinasse,
delivers a saving of 53.2 kg CO2 eq emitted to the atmosphere considering the carried load from
previous process.

65
Table 4.8. Damage assessment for vinasse production (F.U.)
Damage category Unit TOTAL
Human health DALY -0.004
Ecosystem quality PDF*m2*yr -336.144
Climate change kg CO2 eq -53.222
Resources MJ primary 688.575

These are better understood once again considering the benefits of aiming for vinasse as
the main product for a later production of biomethane to be used in the OCM process for bio
ethylene production, leaving as principal coproduct a dehydrated bioethanol stream.
In Fig. 4.9 can be seen the large negative impact in terms of mPt on the human toxicity
field, especially in non-carcinogens effects.

20

-30

-80

-130

-180
mPt

-230

-280

-330

-380

-430

-480

Sugar cane Juice Fodder yeast Cyclohexane Ethanol, without water, in 99.7% solution state Glycerine

Fig. 4.9. Impact assessment weighting per impact category

The total points for human health and other damage categories are presented totalized in
Fig. 4.10 as a weighted result. Here can be clearly observed the total negative impact on human
health mainly due to the avoided bioethanol. This coproduct flow also accounts for the biggest
share in the negative impact observed in ecosystem quality.

66
 90

-10

-110

-210
mPt

-310

-410

-510

-610
Human health Ecosystem quality Climate change Resources
Sugar cane Juice Fodder yeast
Cyclohexane Ethanol, without water, in 99.7% solution state
Glycerine
Fig. 4.10. LCA results weighted per areas of concern

This is better understood once again considering the benefits of aiming for vinasse as the
main product for a later production of biomethane to be used in the OCM process for bio
ethylene production, leaving as principal coproduct a dehydrated bioethanol stream. The human
health area is presented in detail in Table 4.9.

Table 4.9. Life cycle data for human health in Vinasse production stage
Impact category Carcinogens Non- Respiratory Respiratory
(kg C2H3Cl carcinogens (kg inorganics (kg organics (kg
eq) C2H3Cl eq) PM2.5 eq) C2H4 eq)
Sugar cane Juice -7.071 -49.171 0.064 0.003
Fodder yeast 1.265 -0.398 0.105 0.026
Cyclohexane 0.012 0.002 0.000 0.000
Ethanol, without water,
-171.084 -1124.832 -0.323 -0.103
in 99.7% solution state
Glycerin -0.088 0.105 -0.007 -0.005
Total -176.965 -1174.295 -0.161 -0.079

Here, the negative impact in terms of avoided chloroethene emissions once again is
observed, as in the previous process for juice production.
But, order to stablish which of the process has the higher impact on different mid-point
categories displayed before, a results comparison is presented in the next subchapter to have a
better idea on the main contributors.

4.2. Summary of LCA results

For a better understanding of the main impact categories, each one of the process was
accounted for its own impact disregarding the dragged environmental effect carried out by the
previous one. Fig. 4.11 show the effect of each process in releasing GHG to the atmosphere. It
67
is shown how while the agricultural stage and harvesting process of sugarcane has the higher
impact while the production of vinasse delivers a benefit to the environment due to the avoided
emissions from the production of bio ethanol.

30

10

Sugarcane Production Juice Production Vinasse production

-10
kg CO2 eq

-30

-50

-70

-90

Fig. 4.11. Effect of each process in Global warming category

Land occupation was the other selected midpoint category to compare as the production
of biofuels from 1st generation feedstocks has always represent a moral issue due to the use of
arable land for other purpose than the production of food. The results are presented in Fig. 4.12.

150

100
m2org.arable

50

0
Sugarcane Production Juice Production Vinasse production

-50

-100

Fig. 4.12. Effect of each process in Land Use category

As it was expected from the inventory in Table 3.2, the cultivation of sugarcane requires
a large amount of land use, even under the use of new techniques to improve the crops yield.
On the other hand, vinasse production shows savings in land use due to the bio ethanol effluent
as avoided product as can be seen in Table 4.10. This table also shows how the impact of using
yeast in this process as the total benefit is reduced by its influence. However, in Brazilian
biorefineries, yeast is recovered to avoid the use of new raw material, hence, room for
improvement in the modeled scenario is available in this point.
68
Table 4.10. Life cycle data for GHG and land occupation in Vinasse production stage
Impact category Global warming (kg CO2 eq) Land use (m2org.arable)
Sugar cane Juice 27.901733 110.10353
Fodder yeast 75.015774 65.281559
Cyclohexane 0.16186872 0.001748592
Ethanol, without water,
-149.00185 -140.3202
in 99.7% solution state
Glycerin -7.2992229 -5.2811203
Total -53.221693 29.785511

The impact of each process in the different categories for human health area of concern
is presented in Fig. 4.13 alongside with the global warming and land occupation in percentile
points as every single of them has different measure units.

100%

80%

60%

40%

20%

0%

-20%

-40%

-60%

-80%

-100%
Global warming Land occupation Carcinogens Non-carcinogens Respiratory Respiratory
inorganics organics

Sugarcane Production Juice Production Vinasse production

Fig. 4.13. Process influence in relevant Impact categories

The agricultural phase once again is proving to have the highest impact on land use, GHG
emissions and respiratory inorganics due to the use of fertilizers and the required land for crops.

4.3. Sensitivity Analysis

As explained before and seen in Fig. 4.10, the majority of the negative impact (benefit to
the environment) delivered by the production of vinasse is due to bioethanol is considered an
avoided product. To double check the accuracy of the simulate on and the LCI gathered during
this project, comparison between impacts from producing vinasse through the process modeled
and the production of bioethanol in Brazil located in the Ecoinvent inventory within simapro.
To do so, the mass balance ratio must be considered, meaning that for every kg of bioethanol
produced, 15 kg of vinasse is coproduced (see Table 3.3). The comparison screen in simapro
using IMPACT 2000+ method can be seen in Fig. 4.14.

69
 Fig. 4.14. LCA comparison between bioethanol and Vinasse production

Results from this comparison can be seen in Fig. 4.11 (a) in terms of weighted results
showing how the impacts from each one of the analyzed products might overlap in each of the
areas of concern. In Fig. 4.11 (b) the single total score for each process is seen summarizing all
the impacts in the damage categories. While for producing 15 kg of Vinasse, a total score of -
8.73 mPt is obtained, the score for bioethanol production (1 kg) is 9.1 mPt. As the process for
producing vinasse and/or bioethanol considered in this work is the same, it can be considered,
the impact of producing bioethanol under the baseline scenario is the absolute value for vinasse
results.
The small differences in the scores from one production pathway to the other can be
explained by minimal errors in the assumptions and data collection, or a different yield for
bioethanol production from sugarcane considered in the Ecoinvent inventory. Still, the
difference between results could be considered insignificant as it is only 4 % apart from each
other, a result that shows consistency and accuracy in the simulated scenario for vinasse
production in Brazil

(a)
9
7
5
3
1
mPt

-1 Human health Ecosystem quality Climate change Resources

-3
-5
-7
-9
-11

Vinasse Ethanol, without water, in 99.7% solution state, from fermentation {BR}

70
 (b)
9
7
5
3
1
mPt

-1
-3
-5
-7
-9
-11
Vinasse Ethanol, without water, in 99.7%

Human health Ecosystem quality Climate change Resources

Fig. 4.15. LCA interpretation (a) weighted results. (b) single score

Now, for the sensitivity analysis, two types of analysis were conducted. In the first one,
sensitivity to electricity use was studied switching the power consumption from the energy mix
in Brazil to the one available in Latvia to observe if changes in the source of power makes any
difference in the LCA results. Finally, the second sensitivity analysis is referred to the LCA
model comparing the already discussed one using IMPACT 2002+ with a more focused one on
agricultural and industrial processes such as the Environmental Development of Industrial
Products (EDIP 2003). This method was selected as includes the potential dispersion of
substances consequently increasing the exposure effects. This is achieved since EDIP 2003
integrates within it, the Cause effect relation model (CARMEN model) (Hauschild & Potting,
2005). As stated by Hauschild & Potting, (2005), this model is “an integrated assessment model
to analyze and evaluate strategies to reduce nutrient loading of inland waters and coastal seas
in Europe. The model does not contain an assessment of ecological effects but calculates the
change in nutrient loads in ground water, inland waters (river catchments) and coastal seas from
changes in nutrient emissions and supplies”.

4.3.1. Sensitivity to power consumption

As these type of biorefineries are usually powered self-sufficient by using the bagasse in
junction with coal in cofiring plants to produce steam to later be used for electricity generation
(Incauca, 2019 and Morschbacker, 2009), and the flue gas from turbines is used for thermal
needs in the evaporation and distillation processes, the energy required for heating, electricity
and mechanical machinery was not considered within the first analysis. This approach is also
considered by Pereira, et al., (2019). In order to compare the results when and if using electricity
from the energy grid available in Brazil, an LCA was modeled including 12 kWh/ton sugarcane
processed for electricity purposes and 16 kWh/ton for the mechanical requirements under the
milling process (Coordinacion BNDES y CGEE, 2008). The network tree for this simulation
can be observed in Annex 6 while the tree for the simulation using the electricity mix from
Latvia is found in Annex 7.
Table 4.11 shows the difference between weighted results when including electricity
consumption from the grid mix instead of disregarding it. Values in mPt are given in reference
to the functional unit.
By including energy consumption, the negative impact is only reduced slightly, proving
that leaving out of the boundaries the energy consumption is a valid assumption for bioethanol
production in Brazil due to the low energy requirement for conducting the required processes.
71
The impacts caused by the use of electricity in Latvia, are only relevant on climate change and
resources areas, where a difference of 1 mPt is observed.
Furthermore, as mentioned by Khatiwada, et al. (2012), in case of expansion in
boundaries were made for this production pathway, the credits from the use of baggage in
electricity generation could even overlap the total GHG emissions caused by ethanol production
in Brazil. Nevertheless, this boundaries expansion would have to consider several variables and
assumptions such as the electricity produced by the ethanol biorefineries, the technology used
for generation and the type of biomass depending on straw or sugarcane bagasse.

Table 4.11. Damage assessment for Vinasse production (F.U.)

Damage category w/o elec. (mPt) Incl. elec. (BR) (mPt) Incl. elec. (LV) (mPt)
Human health -549.39 -548.006 -547.667
Ecosystem quality -24.538 -24.318 -24.417
Climate change -5.375 -4.914 -3.8544
Resources 4.531 4.9389 6.0483

This results prove that in general terms, the model is not sensitive to the use of electricity
disregarding the country mix selected, as the power consumption per ton of sugar cane
processed to obtain vinasse is low, with only 101 MJ required (see Annex 6 and Annex 7).

4.3.2. Sensitivity to the method

As said before, simulation of the baseline scenario disregarding the electricity
consumption was performed using the EDIP2003 method in order to analyze its particular
results and also to compare the results (within the similar impact categories) with the ones from
IMPACT 2002+. Fig. 4.16 shows the impact categories within this model finding new ones if
compared with the previous method.

100%
80%
60%
40%
20%
0%
-20%
-40%
-60%
-80%
-100%

Sugar cane Juice Fodder yeast Cyclohexane Ethanol, without water, in 99.7% solution state Glycerine

Fig. 4.16. Characterization Results for vinasse production using EDIP2003

The results in terms of mPt for the weighted stage (Fig. 4.17), shows how a large negative
impact is obtained from the bioethanol as avoided product in most of the impact categories. On
the other hand, once again the use of yeast for fermentation delivers most of the impact all over
the categories and the previous process for juice production is responsible for most of the effect
in the bulk waste category as there is no benefit allocated to bagasse under this model.
72
 80
60
40
20
0
mPt
-20
-40
-60
-80
-100

Sugar cane Juice Fodder yeast Cyclohexane Ethanol, without water, in 99.7% solution state Glycerine

Fig. 4.17. Weighted results for impact categories using EDIP2003

As almost all impact categories are different for this model, Table 4.12 was built to show
the LCA result in mid-point units. From this table, can be understood the difference between
models, with EDIP 2003 focusing in impacts caused in air, soil and water rather than more
general and wide categories as the IMPACT 2002+.

Table 4.12. Characterization of impact assessment EDIP 2003

Impact category Unit Total
Global warming 100a kg CO2 eq -38.5387
Ozone depletion kg CFC11 eq 3.07E-06
Ozone formation (Vegetation) m2.ppm.h -1685.26
Ozone formation (Human) person.ppm.h -0.1326
Acidification m2 4.982114
Terrestrial eutrophication m2 -12.0839
Aquatic eutrophication EP(N) kg N -0.10865
Aquatic eutrophication EP(P) kg P 0.001587
Human toxicity air person -2.8E+07
Human toxicity water m3 -101.052
Human toxicity soil m3 -148.434
Ecotoxicity water chronic m3 4235.097
Ecotoxicity water acute m3 553.5091
Ecotoxicity soil chronic m3 49416.02
Hazardous waste kg 0.00104
Slags/ashes kg -0.14362
Bulk waste kg 67.74001
Radioactive waste kg 0.002419
Resources (all) PR2004 0.014563

However, for a better comprehension and to be able to assess how much are the load
savings differences to the environment from one to the other model, Fig. 4.18 and Fig. 4.19
were constructed.

73
 Global warming
0
-10

kg CO2 eq
-20
-30
-40
-50
-60

Impact 2002+ EDIP 2003

Fig. 4.18. Global warming results comparison across models

The main difference is observed in the GHG emissions with a lower saving value of -38
kg CO2eq resulting from the EDIP 2003 method. This means, IMPACT 2002+ finds more
benefits resulting from the baseline scenario in the global warming category. The difference
comes from greater impacts delivered from the bio ethanol production and the yeast use
considered by EDIP 2003.

3.0668E-06
3.0666E-06
3.0664E-06
kg CFC-11 eq

3.0662E-06
3.0660E-06
3.0658E-06
3.0656E-06
3.0654E-06
3.0652E-06
Ozone layer depletion

Impact 2002+ EDIP 2003

Fig. 4.19. Ozone layer depletion results comparison across models

In the ozone layer depletion category, the difference can be considered as zero by paying
attention to the units in the y axis.
The sensitivity analysis reflects that although differences are encountered depending on
the model, they are not considered that apart from each other, especially if compared Fig. 4.17,
with LCA results from Fig. 4.9 using IMPACT 2002+. This way it can be concluded that the
model is also, not sensitive to the method engaged.

74
 CONCLUSIONS
1. As the market for ethylene keeps growing, new production capacities are required to
be deployed especially in the Latin America region to avoid further market imbalance.
2. This new additions in capacity should meet environmental requirements by the use of
cleaner production techniques ensuring the lowest possible impact for the environment
while keeping the economic feasibility.
3. Due to the fact, bio ethylene and fossil fuel-based ethylene, are chemically identical,
the identification and studies for new production pathways are of great interest for the
industry, as no new investment for replacing current equipment is necessary.
4. Since the Oxidative Coupling of Methane has been proved to be a commercial
alternative in the most recent years, the search for a sustainable feedstock of bio-
methane has led to the use of biological wastes for its production. Wastes from the
dairy industry and bioethanol refineries have been used with success.
5. The vinasse, a co-product from bioethanol production when used sugarcane as
feedstock was analyzed to calculate the environmental load of producing it in Brazil.
All data used for modeling and calculations were collected from either scientific papers
or currently available data for bioethanol production from sugarcane in Brazil. Data
was contrasted with other LCAs and recommendations made in reports and handbooks
from several countries in Latin America.
6. From the LCA results, can be seen how the production of vinasse and bioethanol, can
be interpreted as a benefit to the environment when vinasse is intended to be the main
product for biomethane production, leaving bioethanol as an avoided product
delivering a negative impact from the LCA perspective.
7. The modeled system using the LCI collected and the proposal process system is taken
from the biggest bioethanol refinery in Colombia was validated by comparing its
results to the included process for Bioethanol production in Brazil found in the
Ecoinvent 3 database within the simapro software and using IMPACT 2002+
methodology.
8. The higher impact received from sugarcane production is on the ecosystem quality,
triggered by the sugar crops production activity due to the large impact from land use.
It was calculated that 13.8 % of species might potentially disappear on one square
meter for one year.
9. Within the production of bioethanol, bagasse is collected as main “waste” and is used
for cofiring usually in combination with coal to produce steam for further power
generation using CHP turbine systems. The benefit of this use has a great impact on
the energy grid of Brazil, where 6% of total electricity comes from this source. Heat
and electricity produced by CHP units are used in the biorefineries and surplus is then
sold to the national system.
10. Considering bioethanol as an avoided product has a large impact mainly in the Human
health area of concern since carcinogens and non-carcinogens effects are discounted.
11. For the sensitivity analysis, the power required for the bioethanol and vinasse
production was considered and modeled as input from the Brazilian energy grid. As
the energy mix in Brazil already accounts for the 6% of the total mix coming from
sugarcane biorefineries, and most of the electric power in this country is generated
from renewable hydropower dams, the effect on the impact categories compared with
the base simulation might be disregarded. It is worth to notice, the required power for
conducting the whole process was calculated in 0.13 MJ/L ethanol produced, a similar
value used for other LCA studies using corn as feedstock in the United States (Pereira,
et al., 2019).
75
 12. When comparing the results of the impact from the modeled system with the results
from ethanol production in the Ecoinvent inventory, can be concluded that the same
magnitude in terms of endpoints results are obtained for both of them. The difference
between them is the negative impact associated with the vinasse production and the
positive one with the ethanol production, due to the perspective in the production
pathways.
13. It can be said, that the LCA performed under this Master thesis is completely valid for
further studies where the bio ethylene environmental load from production via OCM
using biomethane obtained from AnSBBR needs to be conducted for facilities located
in Brazil.

76
 RECOMMENDATIONS
• Information regarding the wastes generated after the 5-6 cycle of sugarcane harvesting
should be gathered directly from Brazilian plantations in order to include them in the model.
• In the future, infrastructure, spare parts and operation and maintenance practices should be
considered for vinasse production from sugarcane, if a total LCA between production of bio
ethylene is to be compared with the standard production pathways using fossil feedstocks.
• The system boundary can be extended to include the yeast recovery process step, to adjust
the model to the current industrial practices conducted in most biorefineries in Brazil.
• The water consumption value used in the milling process might be susceptible to changes
as new techniques are reducing its use by methodology improvements.
• A sensitivity analysis to fertilizer type could also be performed depending on the crop field
under study to assess the impact change in different categories especially in the agricultural
stage.
• The use of herbicide within the model can also be included if information regarding the
specific one used in Brazil is known. The use of inorganic chemicals would probably have
some repercussion in the areas of human health and ecosystem quality that need to be
considered.

77
 REFERENCES
Abas, M., Akram, Z. & Mohammad, J., 2017. Bioethylene Production from Ethanol: A Review
and Techno-economical Evaluation. ChemBioEng Reviews, 4(2), pp. 71 - 140.

Aguayo, A. T. et al., 2002. Catalyst Deactivation by Coke in the Transformation of Aqueous

Ethanol into Hydrocarbons. Kinetic Modeling and Acidity Deterioration of the Catalyst.
Industrial & Engineering Chemistry Research, 41(17), pp. 4216 - 4224.

Almeida, W., Ratusznei, S., Zaiat, M. & Rodrigues, J., 2017. AnSBBR Applied To Biomethane.
Brazilian Journal of Chemical Engineering, 34(3), pp. 759 - 773.

Aram, K. & Taek, S., 2015. Converting Sugars to Biofuels: Ethanol and Beyond.
Bioengineering, Volume 2, pp. 184 - 203.

Bai, F., Anderson, W. & Moo-Young, M., 2008. Ethanol fermentation technologies from sugar
and starch feedstocks. Biotechnology Advances, Volume 26, pp. 89 - 105.

Bame, D. & Fehler, M., 1986. Observations of long period earthquakes accompanying
hydraulic fracturing. Geophysical Research Letters, pp. 149 - 152.

Bergstra, M., 2004. Catalytic ethylene polymerization, Enschede: University of Twente.

Bittencourt, E. et al., 2014. Economic process to produce biohydrogen and volatile fatty acids
by a mixed culture using vinasse from sugarcane ethanol industry as nutrient source.
Bioresource Technology, Volume 159, pp. 380 - 386.

Broeren, M., 2013. Production of Bio-ethylene. Technology Policy Brief I13.

CGEE, 2009. Descrição do processo produtivo – Fase agrícola. In: L. A. Barbosa, ed. Bioetanol
combustível: uma oportunidade para o Brasil. s.l.:Centro de Gestão e Estudos Estratégicos
(CGEE).

CGEE, 2009. Descrição do processo produtivo – Fase industrial. In: Bioetanol combustível:
uma oportunidade para o Brasil. s.l.:Centro Gestão e Estudo Estratégicos.

Coordinacion BNDES y CGEE, 2008. Chapter 3: Bioethanol production (Spanish). In:

Bioetanol caña de azucar, energia para el desarrollo sostenible. 1 ed. Rio de Janeiro: s.n., pp.
67 - 102.

De Andrade, C. D. et al., 2013. Chapter 6. In: Catalytic process development for renewable
materials. s.l.:John Wiley & Sons, Incorporated, pp. 149 - 154.

Earth System Research Laboratory, 2018. Trends in Atmospheric Carbon Dioxide . [Online]
Available at: https://www.esrl.noaa.gov/gmd/ccgg/trends/ [Accessed 24 October 2018].

Food and Agriculture Organization of the United Nations, 2008. The State of Food and
Agriculture. Rome: Electronic Publishing Policy and Support Branch Communication Division
FAO.
78
Geddes, C., Nieves, I. & Ingram, L., 2011. Advances in ethanol production. Current Opinion
Biotechnologies, Volume 22, pp. 312 - 319.

Gray, K. A., Zhao, L. & Emptage, M., 2006. Bioethanol. Current Opinion in Chemical Biology,
10(2), pp. 141 - 146.

Hansen, A., Zhang, Q. & Lyne, P., 2005. Ethanol-diesel fuel blends—A review. Bioresources
Technologies, Volume 96, pp. 277 - 285.

Harihastuti, N. & Marlena, B., 2018. Bioenergy Potential Based on Vinasse From Ethanol
Industrial Waste to Green Energy Sustainability [Online]. The 2nd International Conference on
Energy, Environmental and Information System (ICENIS 2017), Volume 31, pp. 1 - 3.

Haro, P., Ollero, P. & Trippe, F., 2013. Technoeconomic assessment of potential processes for
bio-ethylene production. Fuel Processing Technology, Volume 114, pp. 35 - 48.

Hauschild, M. & Potting, J., 2005. Spatial differentiation in Life Cycle impact assessment - The
EDIP2003 methodology. s.l.:Danish Ministry of the Environment - Environmental Protection
Agency.

He, C. & You, F., 2016. Deciphering the true-life cycle environmental impacts and costs of the
mega-scale shale gas-to-olefins projects in the United States. Energy Environ. Sci., p. 820 –
840.

Hikita, H., Asai, S., Ishikawa, H. & Honda, M., 1977. The kinetics of reactions of carbon
dioxide with monoethanolamine, diethanolamine and triethanolamine by a rapid mixing
method. The Chemical Engineering Journal, 13(1), pp. 7 - 12.

Holloway, M. D. & Rudd, O., 2013. Fracking: The Operations and Environmental
Consequences of Hydraulic Fracturing. Beverly, MA: Scrivener Publishing.

Hong, J., Zhang, Y., Xu, X. & Li, X., 2014. Life cycle assessment of corn- and cassava-based
ethylene production. Biomass Bioenergy, pp. 67: 304 - 311.

Hong, K.-K. & Nielsen, J., 2012. Metabolic engineering of Saccharomyces cerevisiae: a key
cell factory platform for future biorefineries. Cellular and Molecular life sciences, 69(16), pp.
2671 - 2690.

Humbert, S. et al., 2012. IMPACT 2002+: User Guide, s.l.: Quantis Sustainability counts.

Incauca, S., 2019. Bioethanol Process. [Online] Available at: https://www.incauca.com/wp-

content/uploads/2016/05/ PROCESOS_ESPANOL.pdf [Accessed 14 02 2019].

Ingledew, W., 1999. Alcohol production by Saccharomyces cerevisiae: a yeast primer. In: T.
L. a. D. K. KA Jacques, ed. The Alcohol Textbook: A Reference for the Beverage, Fuel and
Industrial Alcohol Industries. Nottingham: Nottingham University Press, pp. 49 - 87.

International Energy Agency, 2011. Technology Roadmap—Biofuels for Transport, Paris: IEA.

79
Jolliet, O. et al., 2003. IMPACT 2002+: A New Life Cycle Impact Assessment Methodology.
Internation Journal on LCA, 8(6), pp. 324 - 330.

Keller, G. & Bashin, M., 1982. Synthesis of ethylene via oxidative coupling of methane: I.
Determination of active catalysts. Journal of Catalysis, pp. 9 - 19.

Khatiwada, D., Seabra, J., Silveira, S. & Walter, A., 2012. Accounting greenhouse gas
emissions in the lifecycle of Brazilian sugarcane bioethanol: Methodological references in
European and American regulations. Energy Policy, Volume 47, pp. 284 - 397.

Lewandowski, S., 2016. Ethylene - Global. s.l., IHS Markit, pp. 2 - 25.

Licht, F., 2006. World Ethanol and Biofuels Report. Biofuel Feedstock Markets, 26 April.

Liptow, C., T. A. & Janssen, M., 2015. Life cycle assessment of biomass-based ethylene
production in Sweden—is gasification or fermentation the environmentally preferable route?.
Int. J. Life Cycle Assess., pp. 20: 632 - 644.

Litch, F., 2011. Feedstock use for biofuels – the outlook for 2011. World Ethanol & Biofuels
Report, 9(1).

Lovato, G. et al., 2017. Chapter 5. Novel Insights Into The Co-Digestion of Whey With
Glycerin in an Ansbbr: Influent Composition and Concentration, Cycle Length and Feed
Strategy Effect. In: J. A. Daniels, ed. Advances in Environmental Research. s.l.:s.n., pp. 162-
178.

Lovato, G. et al., 2018. Methane Production by Co-Digesting Vinasse and Whey in an

AnSBBR: Effect of Mixture Ratio and Feed Strategy. Applied Biochem. Biotechnol. [Online].

LowCVP, 2004. Well-to-Wheel Evaluation for Production of Ethanol from Wheat, s.l.:
LowCVP Fuels Working Group.

Macedo, I., Leal, M. & Silva, J., 2004. Grennhouse Gases Emissions (GEE) in the bioethanol
production in Brazil; current sitation (Portuguese), Sao Paulo: SMA-Secretaria do Meio
Ambiente de São Paulo.

Madigan, M., Martinko, J. & Parker, J., 2000. Brock biology of microorganisms. 9th ed.
Prentice Hall(NJ): Upper Saddle River.

Madson, P., 2003. Chaper 22. Ethanol destillation: the fundentals. In: K. Jacques, T. Lyons &
D. Kelsall, eds. The Alcohol Textbook. 4th ed. Nottingham: Nottingham University Press, pp.
319 - 335.

Markham, J. et al., 2016. Techno-economic analysis of a conceptual biofuel production process

from bioethylene produced by photosynthetic recombinant cyanobacteria. Green Chemistry,
18(23), pp. 6266 - 6281.

80
Matar, S. & Hatch, L. F., 2001. Chemistry of Petrochemical Processes. Houston, TX.: Gulf
Professional Publishing,.

Mleczko, L. & Pannek, U., 1996. Oxidative Coupling of Methane in a Fluidized-Bed Reactor
over a Highly Active and Selective Catalyst. Industrial & Engineering Chemistry Research,
35(1), pp. 54 - 61.

Mohammad, J. & Lennartsson, P., 2013. Bioethanol Production Process. In: Biofuels
Production. s.l.:John Wiley & Sons, Incorporated, pp. 211 - 253.

Morschbacker, A., 2009. Bio-Ethanol Based Ethylene. Journal of Macromolecular Science,

Part C: Polymer Reviews, 49(79), pp. 79 - 84.

National Comitee for sustainable development of Sugarcane (Spanish), 2015. Transport

Mechanism for sugarcane. Mexico DF.: Conadelsuca.

NCGA – National Corn Growers Association, 2008. Fossil energy use in the manufacture of
corn ethanol. , s.l.: National Corn Growers Association.

Noritaka, M. & Makoto, M., 1997. Heteropolyacid catalysts. Current Opinion in Solid State
and Materials Science, 2(1), pp. 84 - 89.

Pereira, L. et al., 2019. Comparison of biofuel life-cycle GHG emissions assessment tools: The
case studies of ethanol produced from sugarcane, corn, and wheat.. Renewable and Sustainable
Energy Reviews, Volume 110, pp. 1 - 12.

Pizaia, W., 1998. Project, Electric Energy Generation by Biomass, Sugarcane Waste and Waste
(Portuguese), Brasilia: s.n.

Ravanchi, M. T. & Sahebdelfar, S., 2014. Carbon dioxide capture and utilization in
petrochemical industry:. Appl. Petrochem Res., p. 4:63–77.

Rebitzer, G. et al., 2004. Life cycle assessment Part 1: Framework, goal and scope definition,
inventory analysis, and applications. Environment International 30, pp. 701 - 720.

Reddy, B. et al., 2005. Sweet Sorghum – A Potential Alternate raw Material for Bio-ethanol
and Bio-energy. [Online] Available at: http://oar.icrisat.org/1234/1/ISMN-46_79-86_2005.pdf
[Accessed 14 May 2019].

RIRDC, 2008. Annual Report 2007 - 2008, s.l.: Australian Government - Rural Industries
Research and Development Corporation.

Romero, E. R. et al., 2009. Fertilización de la Caña de Azucar: Criterios y Recomendaciones.

In: E. R. Romero, P. A. Digonzelli & J. Scandaliaris, eds. Sugar cane producer Handbook
(Spanish). 1st ed. Tucuman: Estación Experimental Agroindustrial Obispo Colombres, pp. 75
- 83.

81
Scodelaro, F., 2017. Ethylene perspectives in Latin America - Special Report. [Online]
Available at: http://www.ingenieriaquimica.org/articulos/perspectivas-etileno-america-latina
[Accessed 25 October 2018].

Siquiera, T., Albuquerque, J., Ratusznei, S. & Rodrigues, J., 2018. Biomethane Production in
an ANsBBR at Termophilic Conditions from Whey and Vinasse (Portuguese). Sao Paulo, s.n.,
pp. 2-15.

Stünkel, S. et al., 2012. Oxidative Coupling of Methane: Process Design,. Chemie Ingenieur
Technik, 84(11), pp. 1989 - 1996.

Tamers, M., 2006. Distinguishing Between Bio-ethanol and Petroleum Ethanol. Ethanol
Producer Magazine.

TechSci Research report, 2016. Global Ethylene Market By End Use, By Region, Competition
Forecast and Opportunities, 2011 - 2025. s.l.:PR Newswire, (Website:
http://www.prnewswire.com).

The World Bank, 2018. Brazil CO2 increase per capita. [Online] Available at:
https://data.worldbank.org/indicator/EN.ATM.CO2E.PC?contextual=default&end=2014&loc
ations=BR&start=1960&view=chart [Accessed 28 October 2018].

Trading Economics, 2019. Commodity Prices. [Online] Available at:

https://tradingeconomics.com/commodities [Accessed 26 04 2019].

U.S. Department of Agriculture, 2008. Agricultural Statistics 2008, Washington: United States
Government Printing Office.

U.S. Department of Agriculture, 2013. Vinasse Technical Evaluation Report, s.l.: USDA.

Valero-Romero, M. J. et al., 2019. Phosphorus-Containing Mesoporous Carbon Acid Catalyst

for Methanol Dehydration to Dimethyl Ether. Industrial & Engineering Chemistry Research,
Issue 10, pp. 4042 - 4053.

Walter, A. et al., 2014. Brazilian sugarcane ethanol: developments so far and challenges for the
future. WIREs Energy Environ., Volume 3, pp. 70 - 86.

Wyman, C., 1996. Ethanol production from lignocellulosic biomass: Overview. In: Hand Book
of Bioethanol. Washington DC: Taylor and Francis, pp. 11 - 12.

Xiang, D., Qian, Y., Man, Y. & Y. S., 2014. Techno-economic analysis of the coal-to-olefins
process in comparison with the oil-to-olefins process. Appl. Energy, pp. 113: 639 - 647.

Xiong, W. et al., 2015. The plasticity of cyanobacterial metabolism supports direct CO2
conversion to ethylene. Nature Plants 1.

Yang, S. & Hoffman, N. E., 1984. Ethylene Biosynthesis and its regulation in higher plants.
Annual Review of Plant Physiology, Volume 35, pp. 155 - 189.

82
Young, R., Pratt, H. & Biale, J., 1951. Identification Of Ethylene As A Volatile Product Of The
Fungus Penicillium Digitatum.. Plant Physiol., 26(2), pp. 304 - 310.

Yu, C. et al., 2010. Dehydration reaction of bio-ethanol to ethylene over modified SAPO
catalysts. Journal of Industrial and Engineering Chemistry, Volume 16, pp. 717 - 722.

Zaman, J., 1999. Oxidative processes in natural gas conversion. Fuel Processing Technology,
58(2-3), pp. 61 - 81.

Zhao, Z. et al., 2018. Low-carbon roadmap of chemical production: A case study of ethylene in
China. Renewable and Sustainable Energy Reviews, pp. 580 - 591.

Zimmermann, H. & Walzl, R., 1997. Ethylene. In: Ullmann's Encyclopedia of Industrial
Chemistry, 5th Edition VCH. Weinheim, Germany: Wiley-VCH Verlag GmbH & Co. KGaA,
pp. 515 - 525.

83
 ANNEXES

84
Annex 1. Ethanol Production scheme
.
 Annex 2. Detailed Process Flow Diagram.
Sunlight
Water Coal
Fertilizer Harvesting
Land
Water Crops
Wagons Trucks Cropper Machines Sugar Cane
Water
Electricity
Steam
Miller
Water + C.hexane Cyclohexane Baggase
Hydrated ethanol
Bioethanol Sugar Cane Juice
Water Tank Rectification Column Most Column Recovered Juice
Water
Vinasse
Lime
Low Pressure Steam
Recovered Vinasse SO2 Heater
Electricity
Heated Sugar cane Juice
Heat exchanger Wine
Electricity to the Market
Electricity
Recovered Yeast
CO2 Yeast
Clarifier
Clarified Juice
Reactor 5 Reactor 4 Reactor 2
Reactor 3 Reactor1 Sedimentary Mud
Settling Tank
Heated Water
Filtration Process
Electricity
Low Pressure Steam
Mud Waste Paste
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Annex 3. Simapro data entry for sugarcane production.
87
 Annex 4. Simapro data entry for sugarcane juice production.
88
Annex 5. Simapro data entry for vinasse production
89
 Annex 6. Network for vinasse production including energy from the electric grid (Brazil)
90
Annex 7. Network for vinasse production including energy from the electric grid (Latvia)
91