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Bioethanol production plant - pretreatment with diluted acid
Technical Report · January 2015

DOI: 10.13140/2.1.2838.8648
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Gheorghe Falca Sahand Iman Shayan

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Design Proposal:
Project Report
January 2015
Team Members:
Chiara Toni
Martin Cipolla
Gheorghe Falca
Sahand Shayan
Bio-Ethanol Production Plant: Pretreatment with “Diluted Acid”
ASSIGNEMENT:
Ethanol from biomass
Goal: Preliminary design and performance analysis of a section of a cellulosic ethanol

production facility. Biomass pre-treatment is based on “diluted acid” technology.
Case definition: The section to be analysed includes the bioreactor, the ethanol
distillation and dehydration. The biomass pre-treatments, wastewater treatment and
other utilities are outside the battery limits for the process simulation, but should be
considered in the performance analysis.
Input stream:
Biomass Grass straw

Flow-rate 280 000 t/year
Temperature 20 °C
Output (ethanol) specification:
:
Maximum water content 0.2 % mass
Pressure 1.013 bar abs
Temperature 31°C
2
Executive Summary
Global warming is a multi-national concern so there is a great drive to search for alternatives to oil
especially as oil is in finite supply. Bio-ethanol, an important renewable transportation fuel, has been
considered as one of the most promising alternatives to petroleum. In fact bio-fuels produced from
the renewable resources could help to minimize the fossil fuel burning and CO 2 production, since they
have the potential to cut CO2 emission (less than 63%) because the plants they are made from, use CO 2
as they grow, also during photosynthesis. It’s important to underline that the complete combustion of
one litre of petrol results in 2.276kg of carbon dioxide, while in comparison, the complete combustion
of one litre of ethanol results in only 1.511kg of carbon dioxide (the calorific value of petrol is 1.5
times greater than that of ethanol and so 1.5 times the amount of CO 2 will be liberated to produce the
same amount of energy).
Additionally, bio-fuel production along with bio-products, can provide new income and employment
opportunities in rural areas.
Since the 1970’s Brazil has produced bio-ethanol on a large scale and now runs many of its cars on pure
bio-ethanol, thus proving the viability of ethanol as a fuel. It also provides proof that the technology
can work on an industrial scale.
Therefore, lingo-cellulosic feedstocks can offer the potential to provide novel bio-fuels, the so-called
bio-fuels of the ‘second generation’. Produced from ‘plant biomass’, this makes up the majority of the
cheap and abundant non-food materials available from plants.
At its most basic, plant biomass can simply be burned in order to produce heat and electricity.
However, there is great potential in the use of plant biomass to produce liquid bio-fuels. The
production from agricultural by-products could only satisfy a proportion of the increasing demand for
liquid fuels. This has generated great interest in making use of dedicated biomass crops as feedstock
for bio-fuel production.
With this project we want to propose a possible solution based on the production of bio-ethanol from
lingo-cellulosic feedstocks, starting with a biomass pre-treatment based on the “diluted acid”
technology. Moreover we want to underline the presence of several different solutions that can be
adopted in a project of a plant, for this reason we have decided to make the comparison between 2
methods for the dehydration part: the molecular sieve technology and the pervaporation unit.
Different softwares were used in order to obtain a design as close as possible to the reality, in
particular with SuperPro Designer we got an overview of the process, while with Aspen HYSYS we
went into detail for the downstream section.
This report details a proposal for a cellulosic ethanol production facility, to be located in the
Northwest America, because the grass seed production industry in the Pacific Northwest produces
about 2 Mt per year of grass straw as a coproduct. Various species of grasses, with yields of up to 5
tons per acre and containing up to 35% cellulose, are potential feedstocks for ethanol production. The
one takes into account is tall fescue (Festuca arundinacea), for its highest ethanol yields.
A suitable location for a production plant would be Willamette Valley in Oregon: it covers about
500,000 acres under grass seed production!
In this report bio-ethanol is produced from 280.000 t/year of grass straw, from which sugar is
extracted and then fermented to produce the fuel with a maximum water content of 0.2% mass. It can
then be used to fuel cars either by mixing with petrol or neat.
3
The hydrolysis and the fermentation sections were developed using cellulase (which includes 3 major
classes of enzymes as endo-glucanases, exo-glucanases and β-glucosidases), genetically modified
Saccharomyces cerevisiae and a SSCF (Saccharification and Co-fermentation) technology.
Three different analyses were performed: environmental, economical and safety evaluations.
From an environmental point of view the categories most dangerous are Global Warming (emissions to
produce the electrical energy and emissions from the bioreactors are very relevant) and Acidification
(mainly caused by the presence of sulfuric acid which can't be removed in the centrifugation and of
course also by the presence of SOx in the energy production from fossil fuels). Moreover it results
that the ethanol conversion plant required 1306 tons/h of water if molecular sieve is used and 989
tons/h of water if pervaporation unit is applied. The environmental evaluation made for the 2 different
technologies available for dehydration section studied, leads to the same value of categories index;
further, the two technologies analyzed doesn’t emit any substance directly.
An economic analysis has shown how the molecular sieve is the most expensive between the two
dehydration equipment, and how we can gain in 30 years 900 000 $ with the plant with the molecular
sieve and 23 millions dollars with the plant that uses the pervaporation unit.
From a safety point of view we have obtained, as we expected, the highest hazard in the distillation
column, and making the comparison between the molecular sieve and the pervaporation technologies not
a so relevant distinction appears, even if the two hazards are part of 2 different categories of the
Fire and Explosion Index, but they are at the border lines of the distinction.
4
Contents
Chapter 1 :Introduction
1.1 - Bio-fuels ……………………………………………………………………………………………………………………………………… 7
1.2 – Second generation bio-fuels ...........................................……………………………………………………… 8
1.3 - Bio-ethanol as a fuel ...........................................................……………………………………………………… 8
1.4 - The production of Bio-ethanol...........................................……………………………………………………… 9
1.5 – Different pre-treatments...................................................……………………………………………………… 9
1.6 - Location of Plant.................………………………………………………………………………………………………………… 9
1.7 – Grass Straw Composition..………………………………………………………………………………………………………… 9
1.8 - Flowsheet ..........................…………………………………………………………………………………………………………… 9
Chapter 2 : Pre-treatment
2.1 - Heterogeneity of the starting raw materials ........................................................................ 10
2.2 – Lignocellulosic raw materials .................................................................................................... 10
2.3 - Diluted acid pre-treatment......................................................................................................... 11
2.4 – The process..................................................................................................................................... 12
2.4.1 – The conveyor belt........................................................................................................... 12
2.4.2 – The Straw Storage........................................................................................................ 13
2.4.3 – Mixing with recycle........................................................................................................ 13
2.4.4 – Washing (Bulk Flow) ...................................................................................................... 13
2.4.5 – Flow splitter..................................................................................................................... 13
2.4.6 – Shredder.......................................................................................................................... 13
2.4.7 – Stream Mixing................................................................................................................. 13
2.4.8 – Water Mixing .................................................................................................................. 13
2.4.9 – The Sulfuric Acid Storage........................................................................................... 13
2.4.10 – Mixing.............................................................................................................................. 13
2.4.11 – Fluid Flow Pump.............................................................................................................. 13
2.4.12 – Heat exchanger............................................................................................................. 13
2.4.13 – Pre-treatment reactor................................................................................................ 14
2.4.14 – Solid-Liquid separator................................................................................................. 14
2.4.15 – Overliming....................................................................................................................... 14
2.4.16 – pH Adjustment.............................................................................................................. 14
2.4.17 – Centrifugation............................................................................................................... 15
2.4.18 – Mixing............................................................................................................................... 15
Chapter 3 : Hydrolysis and Fermentation

3.1 Enzymatic Hydrolysis . ..................................................................................................................... 16
3.1.1 Cellulolytic Enzymes........................................................................................................... 16
3.1.2 Important Factors in Enzymatic Hydrolysis............................................................... 16.
3.2 Hydrolysis and Fermentation Strategies.................................................................................... 17
3.2.1 - Several strategies.......................................................................................................... 17
3.2.2 – Several Microorganisms .............................................................................................. 18
3.2.3 – The chosen strategy: SCF........................................................................................... 19
3.2.4 In the flowsheet............................................................................................................... 20
5
Chapter 4 : Distillation
4.1 - Introduction...................................................................................................................................... 21
4.2 – Design Procedure............................................................................................................................. 21
4.2.1 - Beer Column........................................................................................................................21
4.2.2 - Distillation Column.......................................................................................................... 24
Chapter 5 : Dehydration
5.1 - Introduction ................................................................................................................................... 27
5.2 - Adsorption Column and Molecular Sieve................................................................................... 27
5.2.1- Design of Adsorption Towers and Molecular Sieve................................................ 28
5.2.2 - Design of Vacuum Pump................................................................................................ 28
5.3 – Continuous Pervaporation ........................................................................................................... 28
5.3.1 - Membrane selection....................................................................................................... 29
5.3.2 - Design of Pervaporation Unit ..................................................................................... 29
Chapter 6 : Wastewater Treatment

6.1 - In the process................................................................................................................................. 30
6.1.1 - COD calculator................................................................................................................. 31
6.1.2 – Anaerobic Digestor ..................................................................................................... 31
6.1.3 - COD calculator............................................................................................................... 31
6.1.4 - Aerobic Bioxidation Unit ............................................................................................. 31
6.1.5 - Belt Filtration ............................................................................................................... 31
Chapter 7 : Economics, Sustainability, Health & Safety

7.1 – Economic Evaluation...................................................................................................................... 33
7.1.1 - Assumptions.................................................................................................................. 33
7.1.2- Molecular Sieve VS Pervaporation Unit................................................................... 33
7.1.3 - NPV calculation............................................................................................................. 34
7.2 – Sustainability: Environmental Impact Evaluation.................................................................... 34
7.2.1 - Goal and scope.................................................................................................................. 35
7.2.2- Functional unit.................................................................................................................. 35
7.2.3 - System boundary and data source.............................................................................. 35
7.2.4- Results................................................................................................................................. 35
7.2.5 - Molecular Sieve VS Pervaporation.............................................................................. 36
7.3 – Health & Safety............................................................................................................................... 36
7.3.1 - Information on Safety.................................................................................................. 36
7.3.2 - Operational safety...........................................................................................................36
7.3.3 – Sulfuric Acid ................................................................................................................... 37
7.3.4 – Ethanol................................................................................................................................37
7.3.5 - DOW Fire and Explosion Index Analysis...................................................................38
7.3.6 - HAZOP.............................................................................................................................. 38
Chapter 8: Conclusions........................................................................................................................... 39
Flow-Sheets............................................................................................................................................... 41
Bibliography................................................................................................................................................ 42
6
Chapter 1 : Introduction
1.1 - Bio-fuels
The OECD (Organisation for Economic Co-operation and Development) defines bio-fuels as "solid, liquid
or gaseous products for conversion of biomass" (OECD, 2002). Traditionally, their use is linked to the
transport sector in replacing fossil fuels, however, in recent years there has been a rapid expansion of
the application field of bio-fuels in the direction of the electric and thermal generation with a
particular focus on the co-generation.
In the current definition of bio-fuel, therefore, it have been exceeded the link with the transport
sector, giving greater emphasis to the heterogeneity of applications. Based on the state of maturity of
the technologies for production and use, bio-fuels are divided into two categories (Eisentraut, 2010):
- The first-generation bio-fuels: are those produced mainly by food crops such as seeds, sugar
cane and vegetable oils. Include bio-diesel, pure vegetable oils, bio-ethanol from cereal crops
and sugar raw materials, bio-ETBE (bio-ethyl-tert-butylether) produced from bio-ethanol and
biogas. Their production and their applications, already begun on an industrial scale, have
margins of improvement in the reduction of production costs, the optimization of the energy
balance, the increase in energy efficiency of the engines and the increase of the percentage of
use in mixture with fossil fuels;
- The second-generation bio-fuels: according to the choice of raw materials and the cultivation
technique, they have the potential to provide additional benefits such as the use of residual
biomass as the starting substrate and the possibility to use, in alternative, marginal land for
the production of energy crop, plant species capable of producing a high quantity of vegetable
biomass even with reduced / or absent input. Include bioethanol from lingo-cellulosic
feedstocks, biohydrogen, the syngas, biomethanol, biodimethylether, bio-MTBE (Biomethyl-
tert-butylether), the bio-butanol and synthetic diesel, obtained through the Fischer-Tropsch
reaction. Their production is not applicable on an industrial scale, but it is still being studied in
experimental facilities and laboratory.
1.2 – Second generation bio-fuels

The second-generation bio-fuels have in common the ability to be produced from lignocellulosic
biomass at a reduced cost, or even zero. Although the production technologies are not yet optimised,
the second-generation bio-fuels are considered very promising, as they constitute a concrete tool for
reducing the cost of production of bio-fuels, which currently are penalized compared to the fossils
competitors.
The second-generation bio-fuels are not yet produced in commercial form, but a considerable number
of pilot and demonstration plants have been announced in recent years, with research activities taking
place mainly in North America, Europe and some emerging countries such as Brazil, China, India and
Thailand (Eisentraut, 2010).
Current projections of the IEA (International Energy Agency) see a rapid increase in demand for bio-
fuels, in particular for second generation, in an energy sector that aims to stabilize atmospheric CO 2
concentration of 450 parts per million (ppm) (IEA , 2008).
The table below shows the energy balances of the most common fuels of first and second generation:
the energy balance is the ratio between the energy provided by the bio-fuel and the energy used in its
production process. Higher is this ratio, greater is the energy benefit that the bio-fuel allows to
achieve.
7
Bio-fuels Energy Balance Energy Balance

with byproducts without byproducts
Bio-diesel from sunflower 2,0 3,1
Bio-diesel from colza 1,7 3,0
Pure vegetable oils from sunflower 2,8 4,3
Pure vegetable oils from colza 1,8 3,4
Bio-ethanol from beet 1,1 2,2
Bio-ethanol from sweet sorghum 1,2-1,4 2,4
Bio-ethanol from corn 1,0-1,1 2,2-2,5
Bio-ethanol from lingo-cellulosic biomass 1,8 5,6
Bio-ETBE from seed 0,8 1,2
Bio-ETBE from sweet sorghum 1,0 1,7
Bio-ETBE from corn 0,8 1,2
Bio-ETBE from lingo-cellulosic biomass 1,1 1,5
Bio-gas 2,5-6,7 -
1.3 - Bio-ethanol as a fuel

Bio-ethanol is ethyl alcohol (C2H5OH), a renewable energy source produced by fermentation of sugars
present in biomass and it is characterized by a high energy content (27 MJ/kg). It is one of the
alternatives to petroleum, in fact it has a behaviour similar to gasoline and can replace it in the feeding
of “Otto Cycle” engines.
Over last decade, bio-ethanol production has increased from 6.2 (year 2000) to 50 billion litres/year
(year 2010) in United States. The number of ethanol production plants have increased exponentially.
Most of this growth in ethanol has been from first generation corn ethanol: in this case bio-ethanol is
produced using an energy crop such as sugarcane, sweet sorghum, corn, cassava, wheat or constitute
from which sugar is extracted and fermented to produce the fuel. Ethanol can be used as
transportation fuel in existing gasoline vehicles after blending with gasoline, such as E10 - a mixture of
10% ethanol and 90% of gasoline by volume. In the European Union, at present, bio-ethanol is used in
mixture with gasoline at 5% in volume, while in USA and in Canada it is extended to 20%.
However, challenges such as capacity limitations, for example feedstock availability and supply, high
feedstock prices, land and fresh water use, intensive agricultural inputs have led to investigation of
second generation bio-fuels. Lignocellulosic biomass due to their abundance and low cost, are potential
alternatives to serve as feedstock for the second generation ethanol production.
1.4 - The production of Bio-ethanol

Lignocellulosic feedstocks are composed of mainly cellulose, hemicellulose, lignin, extractives and ash
consisting of inorganic minerals. Production of cellulosic ethanol via biological conversion consists of
three critical steps:
- pretreatment of biomass: several pretreatment methods have been investigated by
researchers for degradation of hemicellulose and lignin and to break the crystalline structure
of cellulose. Pretreatment techniques are mainly classified as: physical, chemical (e.g. dilute
acid or alkali), physio-chemical (e.g. steam explosion), and biological pretreatments (e.g. using
white rot fungi);
- hydrolysis of sugar polymers (cellulose, hemicellulose etc.) to sugar monomers: Hydrolysis of
sugar polymers can be achieved chemically by using acid or biologically using enzymes.
Enzymatic hydrolysis is favored over acid hydrolysis due to lower energy consumption (natural
gas, electricity), mild operating conditions, high sugar yields, and lower capital and maintenance
cost of equipment;
- fermentation of sugar monomers to ethanol.
8
1.5 – Different pre-treatments

The pre-treatment can be made with different methodologies:
- with NaOH: NaOH is used in aqueous solution at 8-12% in weight; the pre-treatment is
conducted at a temperature of 80-120°C with a residence time of 30-60 minutes. This
technique has very high costs due to the use of chemicals reagents and to the security
measures in the stages of storage and handling;
- Via steam explosion: the biomass is saturated with water, by the action of water vapor at
pressure (1.5 to 4.0 MPa) and high temperatures (180-230 °C) for a variable time (1-10
minutes). The biomass is then extruded in a reactor at atmospheric pressure, where it
undergoes a rapid expansion. The conditions imposed have also the effect of triggering a
partial hydrolysis of the chains of cellulose and hemicellulose. This pre-treatment is
characterized by a high energy absorption.
- By steam explosion with sulfur dioxide: sulfur dioxide, used in the gas form, has the effect of
acidifying the biomass before subjecting it to the steam explosion pre-treatment and to
favour the onset of hydrolysis of cellulose and hemicellulose. The use of reagents and the
absorption energy make the cost of pre-treatment very high;
- Through the process of "Ammonia Fiber Explosion" (AFEX): biomass is subjected to the action
of ammonia at a temperature of 27 ºC and a pressure of 1.24 MPa. The subsequent abrupt
pressure reduction causes the rapid expansion of pretreated biomass. The costs are very high
and can be reduced by replacing ammonia with carbon dioxide as the supercritical fluid, by
operating at values of pressure of 7.6 to 20.7 MPa;
- Pre-biological treatment: employs the use of microorganisms that break down the cell wall
degrading lignin. In particular, some basidiomycetes ligninolitici are in course of study.
- With diluted acid: is our case of study!
Dilute acid pretreatment is one of the extensively investigated method to remove the hemicellulose
and for structural breakdown of lignocellulosic biomass. During this pretreatment, biomass is treated
at different combinations of temperatures (100-290°C) and residence times (few seconds to several
hours). During hydrothermal pretreatment, most of the hemicellulose is hydrolyzed to sugar monomers
and becomes soluble. Some fraction of cellulose may be depolymerized into glucose. A fraction of lignin
is dissolved and/or redistributed. Externally added acid (0.05-5%) which acts as catalyst during dilute
acid hydrolysis.
1.6 – Location of Plant

Grass straw is co-product of grass seed production and a potential feedstock for biofuel production
due to high cellulose content (up to 31%). Grass seed production is concentrated in the states of
Oregon, Washington, and Idaho. In Oregon, about 0.88 million metric tons/year of grass straw is
available as a co-product from grass seed production. A suitable location for a production plant would
be Willamette Valley in Oregon: it covers about 500,000 acres under grass seed production!
1.7 – Grass Straw Composition

There are different types of grass straw, but for our project we have chosen Tall fescue (Festuca
arundinacea) straw. It is considered as a potential biomass for ethanol production as it is a major grass
seed crop in Willamette Valley, Oregon. Tall fescue seed production yields are about 11.9 Mg/hectare
of straw. Straw from tall fescue contains about 30% cellulose, 20% hemicellulose and 14% lignin. Xylan
is the main component of hemicellulose (82%).
The compositions used come from a study made by Kumar and Murthy in “Pretreatments and Enzymatic
Hydrolysis of Grass Straws for Ethanol Production in the Pacific Northwest U.S”. Solid, ash, protein,
extractives, structural carbohydrates, and lignin were determined using National Renewable Energy
Laboratory, standard laboratory-analytical procedures (NREL, 2010).
1.8 – Flowsheet: The complete flow-sheets of the project are attached in the last pages.
9
Chapter 2 : Pre-treatment
2.1 – Heterogeneity of the starting raw materials

Bio-ethanol is produced during the fermentation of carbohydrates, so for its production very
heterogeneous raw materials can be used, both with a residual nature, both derived from dedicated
crops (Pin and Vecchiet, 2008).
Among them are worth mentioning:

- raw materials rich in simple sugar (eg glucose, sucrose, fructose, fructans): molasses, the by-
products of the production of fruit and vegetable and wine, sugar beet, sweet sorghum, sugar
cane, the Jerusalem artichoke;
- raw materials rich in starch: the residues of potato processing, cereals;
- raw materials rich in cellulose and hemicellulose: agro-forestry residues, the common reed,
miscanthus, fiber sorghum, poplar.
The heterogeneity of the starting raw materials results in a considerable diversification of production
processes. For this reason, their discussion is addressed, articulating the production chain in three
sections:
- sugar, for the processing of raw materials rich in simple sugars;
- starch (or starchy), for the processing of raw materials rich in starch;
- lignocellulosic (second generation bioethanol), for the conversion of raw materials rich in
cellulose and hemicellulose.
The three sections of the chain differ significantly, both for the technological contents (modest for
the sugar section, very high for the ligno-cellulose section), both for the maturity of the process
(good for sugar and starch sections, poor for the lignocellulosic section). The divergence between the
processes is considerably damp in post-fermentation (distillation and dehydration).
2.2 – Lignocellulosic raw materials

The lignocellulosic biomass is mainly composed of cellulose (40-50% by weight), hemicellulose (20-25%
by weight) and lignin (15-30 by weight), as shown in the figure below (Pin and Vecchiet, 2008); are
present, also the ashes (1-5% by weight).
The lignocellulosic section for the production of bio-ethanol is burdened with a complexity that
penalizes it compared to the other sections and that justifies the current state of technological
immaturity. In the cell wall, in fact, hemicellulose and cellulose, convertible into bio-ethanol, are firmly
structured with lignin, not transformable by microbes in ethyl alcohol. Some simple sugars, released
during the degradation of hemicellulose (xylose, arabinose, mannose), moreover, are difficult to
ferment for most of the yeast strains normally used for the production of bio-ethanol. Scientific
research is making a major investment in this sector to overcome numerous obstacles (Lynd et al.,
2002; Hahn et al., 2006).
The pre-treatment of biomass is crucial to disrupt the cell wall structure and separate the cellulose
and hemicellulose from lignin.
The pretreatment is used to decompose the lignocellulosic species, if there were no pre-treatment,
would be much more difficult to attack cellulose in order to hydrolyse it, since it is protected from the
package of lignin owning also a crystalline structure very tidy and compact which makes it indissoluble.
The hemicellulose is also protected from lignin, however it has an amorphous structure, so untidy
inside: a bit as the threads of a ball of wool between which many blanks remain. Therefore
hemicellulose, subjected for a certain time under high temperature conditions and impregnated with
water vapor, solubilizes releasing in solution pentose sugars from which is made up. The cellulose
10
instead remains equal and to get glucose first it must be deconstructed to free it from lignin, then
split it with the appropriate enzymes (cellulase) which can hydrolyse the chains.
2.3 – Diluted acid pre-treatment

Pretreatment of lignocelluloses is intended to disorganize the crystalline structure of macro and
microfibrils, in order to release the polymer chains of cellulose and hemicellulose, and/or modify the
pores in the material to allow the enzymes to penetrate into the fibres to renders them amenable to
enzymatic hydrolysis. Pretreatment should be effective to achieve this goal, avoid degradation or loss
of carbohydrate, and avoid formation of inhibitory by-products for the subsequent hydrolysis and
fermentation: obviously, it must be cost-effective.
Dilute-acid hydrolysis is probably the most commonly applied method among the chemical hydrolysis
technologies. It can be used either as a pretreatment preceding enzymatic hydrolysis, or as the actual
method of hydrolysing lignocellulose to the sugars. The dilute-acid pretreatment can achieve high
reaction rates and significantly improve cellulose hydrolysis. With this method about the 90% of the
hemicellulose sugars is recover. The hemicellulose, mainly xylan or mannan, accounts for up to a third
of the total carbohydrate in many lignocellulosic materials. Thus, hemicellulose recovery can have a
highly positive effect on the overall process economics of ethanol production. One of the main
advantages of dilute-acid hydrolysis is achieving high xylan to xylose conversion yields, which is
necessary to achieve favourable overall process economics in ethanol production from lignocellulose. On
the other hand, a main disadvantage of this pretreatment method is the necessity of neutralization of
pH for the downstream enzymatic hydrolysis. Furthermore, different chemical inhibitors might be
produced during the acid pretreatment which reduce cellulase activity, and therefore, water wash is
necessary for the pretreated biomass before enzymatic hydrolysis.
The ethanol production process using dilute acid pretreatment and SSCoF is shown in the 2 flowsheets
attached in the last pages. During this process, grass straw is treated in a dilute H 2SO4 solution (1%
w/w) at 180°C with a 15 min residence time in the reactor. The heated slurry is immediately cooled by
exchanging heat with input stream to reactor. The pretreatment process is indicated by a single
reactor as there is not much information available regarding commercial scale pretreatment reactor
design. In practice this process would contain a series of equipment: screw conveyors, tanks and
reactor. Solid and liquid portions are separated using pneumapress pressure filter to facilitate the
detoxification. Overliming process is used as the detoxification or ‘conditioning’ step. During the
overliming process, liquid fraction is adjusted to 10.0 pH using Ca(OH)2. Subsequently, the pH is
11
adjusted to 5.0-6.0 pH by adding H2SO4. The liquid stream is combined with the solid fraction and is
fed to SSCoF process.
But let’s go in deep in this process.
2.4 – The process

Once ready, the biomass is cut and then left to dry in the field, or it can be transported to the plant
wet. For the collection of the biomass we can distinguish between pulping and baling; the mechanical
collection starts with a classical chopping system and then it’s stored.
The ratio cost/benefit has to be assessed case by case. Biomass comes now to be part of the actual
bio-ethanol production process, through the first stage, called pretreatment.
Collection in 2 phases: The mechanical collection takes

Pulping… place with a classical chopping
system
Discharge of the sheared

…and baling biomass in a heap
Final storage of
biomass
The washed, shredded biomass is fed to pretreatment and first steamed with low-pressure steam in a
presteamer to about 100°C. This steam removes non-condensables that can take up space in the
reactor and allows about one-third of the total pre-hydrolysis reaction heat requirement to be
satisfied by low-pressure steam. The presteamer is fed by a set of screw conveyors with variable
frequency drives to vary the feed rate as the process may dictate.
2.4.1 – The conveyor belt

A conveyor belt is the carrying medium of a belt conveyor system, it consists of two or more pulleys
with an endless loop of carrying medium that rotates around them. One or both of the pulleys are
powered, moving the belt and the material on the belt forward. There are two main industrial classes
of belt conveyors, in this case we are talking about the ones used for bulk material handling, such as
those used to transport large volumes of resources and agricultural materials.
In our case it conveys solids with a specific loading rate of 19,00 (MT/h)/cm.
12
2.4.2 – The Straw Storage

The straw is stored continuously with a residence time of 10 hours, under adiabatic conditions, with a
final temperature of 26,7°C and a pressure of 1,013 bar.
2.4.3 – Mixing with recycle

It is then present a mixer in order to mix flow of different streams, in particular it is used to recycle
the components coming from the successive units, in order to make the process more efficient.
2.4.4 – Washing (Bulk Flow)

This equipment washes the grass straw with 100,53 L/h of water (25°C) at a throughput of 12123,99 kg/h, in
order to separate part of ashes, extractives and trash from the process stream.
2.4.5 – Flow splitter

It is used to split the process stream, in order to send the 30% of the total volume back to the mixer.
2.4.6 – Shredder
An industrial shredder is a machine used for reducing the size of all kinds of material. Industrial
shredders come in many different variations and sizes. They can be equipped with different types of
cutting systems: single-shaft, two-shaft, three-shaft and four-shaft cutting systems. These
shredders are all slow-speed systems, in contrast to hammer mills which are generally high-speed
systems. The temperature of the inlet and outlet streams is 26,7°C.
2.4.7 – Stream Mixing

It is used to mix the process stream with the flow of water and ethyl alcohol coming from the
downstream process, transported into a single current at a temperature of 25,37°C and a pressure of
1,013 bar.
2.4.8 – Water Mixing

The water mixing adjusts flow of Add-In stream and mixes it with the process stream to have the
85% wt of water in the outlet stream. The pure water used in input has a temperature of 25°C and the
output stream reaches a final temperature of 25,16°C. The pressure remains unchanged: 1,013 bar.
2.4.9 – The Sulfuric Acid Storage

The Sulfuric Acid Storage is a container for the Sulfuric Acid used in the pre-treatment. It is stored
continuously with a residence time of 1 hours, under adiabatic conditions, with a final temperature of
25°C and a pressure of 1,013 bar. Concentrated sulfuric acid is diluted with evaporator condensate
until the mixture (the total water, including steam and acid) in the reactor is 1% wt sulfuric acid.
2.4.10 – Mixing
It adjusts the flow of the sulfuric acid coming from the storage tank and it is used to mix it with the
process stream, at a temperature of 25°C and a pressure of 1,013 bar, in order to have 1% wt of
sulfuric acid in the outlet stream. After the mixing the temperature reached is 25,16°C and the
pressure of 1,013 bar.
2.4.11 – Fluid Flow Pump

A pump is a device that moves fluids or sometimes also slurries, by mechanical action. In our case it is
used to increase the pressure by 10 atm, passing from a pressure of 1,013 bar to one of 11,146 bar.
2.4.12 – Heat exchanger

This unit exchanges heat under counter-current flow to a minimum approach temperature of 10°C,
passing from a process stream of 25,27°C to one of 51°C, using a recycled stream with a temperature
of 180°C.
13
2.4.13 – Pre-treatment reactor

This unit executes some reactions, reacting continuously with a working to vessel volume ratio of 100%,
at 180°C and a pressure of 11,146 bar.
The reactions are the following (some approximations and simplifications made in SuperPro were used):
162 Cellulose + 18 H2O  180 Glucose
132 Hemicellulose + 18 H2O  150 Xylose
180 Glucose  126 HMF + 54 H2O
150 Xylose  96 Furfural + 54 H2O
1 Lignin  1 Soluble Lignin
1 Extractives  1 Soluble Extractives
2.4.14 – Solid-Liquid separator

A separation process is a method to achieve any mass transfer phenomenon that converts
a mixture of substances into two or more distinct product mixtures. Separations are carried out based
on differences in physical properties, in fact it’s a solid/liquid separator. The solid-liquid separator
used is the Pneumapress, a pressure belt filter press, that provides the best recovery of solids, and
solubles with minimal wash water. The Pneumapress pressure filter provides automated batch liquid-
solid separation by forcing compressed air through the biomass slurry and filter media to displace
liquid, maximizing the solid content of the cake on the filter. The cycle times of this batch unit are
typically quite short (<10 minutes).
The inlet flow has a temperature of 51°C and a pressure of 1,013 bar, while the outlet streams reach
both 52,78°C.
2.4.15 – Overliming
Overliming is an effective way of conditioning to reduce the toxicity of hydrolyzates generated from
pretreatment of lignicellulosic biomass for ethanol production. In this process the reagents react
continuously with a working to vessel volume ratio of 90%, under adiabatic conditions (in fact the
process stream enters with a temperature of 52,78°C and exits at 52,91°C) and pressure of 1,013 bar.
Calcium Hydroxide (Lime), the neutralizing agent, is used at an excess of 5% and with a temperature of
25°C in order to get a pH equal to 10.
In this unit two main reactions happen:
- one between Calcium Hydroxide and Sulfuric Acid:
74,09 Calcium Hydroxide + 98,08 Sulfuric Acid  136,14 CaSO4 + 36,03 H2O
- One between the product just formed and water:

136,14 CaSO4 + 36,03 H2O  172,17 Gypsum
2.4.16 – pH Adjustment
In this process the reagents react continuously with a working to vessel volume ratio of 90%, under
adiabatic conditions (in fact the process stream enters with a temperature of 52,91°C and exits at
52,91°C) and pressure of 1,013 bar. Sulfuric Acid, the neutralizing agent, is used at an excess of 5%
and with a temperature of 25°C in order to get a pH equal to 5-6.
In this unit two main reactions happen:
- one between Lime and Sulfuric Acid:
74,09 Calcium Hydroxide + 98,08 Sulfuric Acid  136,14 CaSO4 + 36,03 H2O
- one to give rise to gypsum:

136,14 CaSO4 + 36,03 H2O  172,17 Gypsum
14
2.4.17 – Centrifugation
Centrifuge is used with a rate of 77107 L/h to remove the solid part. As utilities, chilled water with an
inlet temperature of 5°C and an outlet of 10°C is used. We have chosen this equipment mainly for an
economic issue, comparing costs with a second possible solution, the use of hydrocyclones.
A hydrocyclone is a device to classify, separate particles in a liquid suspension based on the ratio of
their centripetal force to fluid resistance, so useful in our case. This ratio is high for dense (where
separation by density is required) and coarse (where separation by size is required) particles, and low
for light and fine particles. However in this project, in order to obtain a satisfactory separation, too
many hydrocyclones would be needed.
2.4.18 – Mixing
It is used to mix the process stream (T= 52,91°C) with the second outlet stream coming from the
solid/liquid separator at a temperature of 52,78 °C and a pressure of 1,013 bar. After the mixing the
temperature reached is of 52,88°C and the pressure remains equal to 1,013 bar.
15
Chapter 3 : Hydrolysis and Fermentation
3.1 Enzymatic Hydrolysis

Enzymatic hydrolysis of cellulose to glucose is carried out by cellulase enzymes that are highly specific
catalysts. The hydrolysis is performed under mild conditions (pH 4,5-5,0 and temperature 40-50°C).
Therefore, one may expect low corrosion problems, low utility consumption and low toxicity of the
hydrolyzates as the main advantages of this process.
3.1.1 Cellulolytic Enzymes

Enzymatic hydrolysis of cellulose and hemicellulose can be carried out by highly specific cellulase and
hemicellulase enzymes. This group includes at least 15 protein families and some subfamilies. Enzymatic
hydrolysis of cellulose consists of the cellulase adsorption onto the surface of the cellulose, the
biodegradation of cellulose to glucose is generally accomplished by synergistic action of at least 3
major classes of enzymes: endo-glucanases, exo-glucanases and β-glucosidases. These enzymes are
usually called together cellulase or cellulolytic enzymes.
The endo-glucanases attack the low crystallinity regions of the cellulose fibre and create free chain-
ends. The exo-glucanases further degrade the sugar chain by removing cellobiose units (dimmer of
glucose) from the free chain-ends. The produced cellobiose is then cleaved to glucose by β-
glucosidase. This enzyme is not a cellulase, but its action is very important to complete the
depolymerization of cellulose to glucose. Since hemicellulose contains different sugar units, the
hemicellulytic enzymes are more complex. Fortunately there are several species of bacteria that are
able to produce cellulases and hemiellulases.
3.1.2 Important Factors in Enzymatic Hydrolysis

Substrate concentration and quality, applied pretreatment method, cellulase activity and hydrolysis
conditions such as temperature, pH and mixing are the main factors in enzymatic hydrolysis of
lignocellulosic materials. The optimum temperature and pH are functions of the raw material, the
enzyme source and hydrolysis duration. The optimum temperatures and pH of different cellulases are
usually reported to be in the range of 40-50°C and pH 4-5. However, the optimum residence time and
pH might affect each other. Generally a Citrate buffer (0.05 M) is used to maintain the pH at 4.8,
supplemented with 0.04 mg mL-1 tetracycline to prevent microbial contamination. At predetermined
time intervals (3, 6, 12, 24, 48, 72, 96, and 120 h), 1.0 mL of liquid is drawn and centrifuged (10,000
rpm for 5 min) to measure the glucose concentration at that time.
Hydrolysis yields of the pretreated grass straw samples can be calculated in terms of glucose released
during enzymatic hydrolysis in two different steps:
1) subtracting the glucose released during pretreatment from the initial glucose content in the grass
straw, but it doesn’t consider the formation of fermentation inhibitors, such as hydroxymethylfurfural
(HMF), during the pretreatment process.
Estimated potential glucose =

Glucose content in raw biomass - Glucose in pretreatment liquid
2) using the enzymatic assay described below

Hydrolysis yield (%) =
(Glucose in sample at any time/ Estimated potential glucose) x 100
One of the main factors that affect the yield and initial rate of enzymatic hydrolysis is the substrate
(cellulose/hemicellulose) concentration in the slurry solution. High substrate concentration can cause
substrate inhibition, which substantially lowers the hydrolysis rate. The extent of the inhibition
16
depends on the ratio of total enzyme to total substrate. Problems in mixing and mass transfer also
arise in working with high substrate concentration. The ratio of enzyme to substrate used is another
factor in enzymatic hydrolysis. Obviously application of more cellulase, up to a certain level, increases
the rate and yield of hydrolysis. However, increase in cellulase level would significantly increase the
cost of the process.
Moreover addition of surfactants, carefully selected, during hydrolysis can modify the cellulose
surface properties, in fact an important effect in a process for lignocellulose conversion is the
possibility to lower the enzyme loading. The most effective surfactant is polyethylene glycol, which
increases the enzymatic conversion from 42% to 78% in 16 hours. One reason for this effect might be
the adsorption of surfactants to lignin, which prevents unproductive binding of enzymes to lignin and
results in a higher productivity of the enzymes. The recycling of cellulase enzymes is one potential
strategy for reducing the cost of the enzymatic hydrolysis during the bioconversion of lignocellulose
to ethanol. However, presence of solid residuals (mainly lignin) and dissolution of the enzymes in the
hydrolyzates make the enzymes difficult to separate.
It should be kept in mind that endo-glucanase and exo-glucanase should diffuse into lignocelluloses and
be adsorbed to the surface of the particles in order to initiate hydrolysis and convert the cellulose to
cellobiose. Then in the aqueous phase it is converted to glucose by β-glucosidase.
Hydrolysis yield with time for tall fescue

(HW = hot water, DA = dilute acid, and D.Alk = dilute alkali).
3.2 Hydrolysis and Fermentation Strategies

3.2.1 - Several strategies
Several systems are employed in processing and fermenting lignocellulosic hydrolyzates: batch, fed-
batch, simultaneous saccharification and fermentation (SSF), simultaneous saccharification and co-
fermentation (SSCF), separate hydrolysis and fermentation (SHF), consolidated bioprocessing (CBP),
drop add, or continuous cascades. These processes frequently involve enzymatic (or microbial)
hydrolysis comprising: production of cellulases and hemicellulases; hydrolysis of pre-treated biomass;
fermentation of hexose (glucose, mannose, galactose) and pentose (xylose, arabinose) sugars.
17
For yeast processes, significant challenges remain open in the field of yeast strains for lignocellulosic
hydrolyzates. There are also major challenges presented in such hydrolyzates due to the presence of
chemicals that are toxic to the fermentative microorganisms (yeasts and bacteria). The sources of
these chemicals are outlined in the figure below.
3.2.2 – Several Microorganisms

Fermentation process generally is accompanied by using yeasts or bacteria as microorganisms of
bioprocess. We can summarize some yeasts and ethanologenic bacteria used in bioethanol
fermentations in the list below[1]:
YEASTS:
 Saccharomyces cerevisiae: Predominant bioethanol microbe capable of fermenting the main
sugars derived from first-generation feedstocks (eg. glucose, fructose, sucrose, maltose)
under large-scale industrial production conditions.
o Disadvatages: Incapable (unless genetically modified) of fermenting pentose sugars (eg.
xylose, arabinose) derived from second generation lignocellulose feedstocks. Ethanol
productivities of GM strains fermenting xylose are quite low 0.23-0.34 g/g sugar.
 Pichia stipitis, Candida shehatae, Kluyveromyces marxianus, Pachysolen tannophilus: Non-
Saccharomyces yeasts capable of fermenting pentose sugars (eg. xylose, arabinose) derived
from second generation lignocellulose feedstocks.
o Disadvantages: not particularly ethanoltolerant yeasts and await exploitation for large-
sclae industrial fermentation processes.
 Hansenula polymorpha: High temperature xylose fermentations (Ishchuk et al, 2008)
o Disadvantages: Un-tested on industrial scale.
 Dekkera bruxellensis: “Wild” yeast found in distillery fermentations that may be capable of
ethanol production under stressful conditions.
o Disadvantages: not yet fully commercialised and awaits further research prior to
industrial exploitation.
18
[1] Graeme M.Walker; Bioethanol: Science and technology of fuel alcohol; Ventus Publishing Aps, 2010
Candida krusei: Ethanolgenic yeast producing low levels of secondary fermentation metabolites
such as succinic acid.
o Disadvantages: As with D. bruxellensis.
ETHANOLOGENIC BACTERIA:
 non-GM Strains : Numerous ethanologenic bacteria are known, some of which (eg. Zymomonas
mobilis has a productivity of 0,46 g/g sugar) produce ethanol more effectively than yeast.
Klebsiella oxytoca also has potential with an ethanol productivity between 0.34-0.42 g/gsugar.
May not survive the stressful environment in large-scale bioethanol plants, and ethanol
productivities are generally quite low.
 GM Strains (for lignocellulose hydrolysates): Geobacillus stearothermophilus is a thermophile
which ferments C5 and C6 sugars including short polymers at temperatures in excess of 60°C
with yields ~80% theoretical maximum. It has been genetically modified to produce ethanol
rather than lactate and formate [2]. Not particularly ethanol tolerant (~5% v/v). Escherichia
coli (with Z. mobilis genes encoding pyruvate decarboxylase and alcohol dehydrogenase) and
Erwinia chrysanthemi (with pyruvate decarboxylase genes) also have potential.
The choice is made based on the desirable characteristics required for the fermentation, which are
represent in the figure below
3.2.3 – The chosen strategy: SSCF

Among the several strategies to perform hydrolysis and fermentation, the one that we have chosen is
the SSCF, namely Saccharification and Co-Fermentation, in which co-fermentation refers to the
fermentation of both five-carbon and six-carbon sugars to ethanol.
The 2 different processes of this area (SSCF) are:
 saccharification of the remaining cellulose to glucose which is done by cellulase enzymes
 fermentation of the glucose and other sugars from dilute acid pretreatment of hemicelluluse
to ethanol which is done by Saccharomyces cerevisiae.
The hydrolysed hemicellulose during pretreatment and the solid cellulose are not separated after the
pretreatment, allowing the hemicellulose sugars to be converted to ethanol together with the SSF
(Simultaneous Saccharification and Fermentation) of the cellulose.
The SSCF process is considered to be an improvement to SSF and is meanwhile being tested at pilot
scale by the U.S. Department of Energy. In fact in SSFC process it is suggested to ferment both
hexoses and pentoses in a single bioreactor with a single microorganism, and not 2 vessels with
different microorganisms as in SSF. Therefore, only a single fermentation step is required to process
hydrolysed and solid fractions of the pretreated lignocellulose.
19
[2] TMO: Converting Low value waste into high value energy; www.tmo-group.com
Nowadays a lot o studies in lab-scale are made with Zymomonas mobilis, but in this project, in order to
co-ferment glucose and xylose, genetically modified Saccharomyces cerevisiae is used.
3.2.4 In the flowsheet

Let’s go in deep in this part using the data coming from our project made on SuperPro Designer.
First the stream coming from the last mixer of the pretreatment enters in a cooler to obtain at the
exit a temperature of 35 °C, suitable for the next mixing with the cellulase. This last is stored
continuously, with a residence time of 5 hours at 11°C and at ambient pressure. The mixer is used to
adjust the two flows with a mass ratio between the two of 0,25. We get a current at 34°C that is
ready now to be sent to the SSCF reactor (6 bioreactors that work under batch conditions are used in
this process according to calculations of the software SUPERPRO DESIGN ), which works continuously
at 35°C and at 1 atm with a vessel volume ratio of 90%. Other two streams are added into the reactor:
the one that carries yeasts (T=25°C) and one of DAP (diammonium phosphate) a fermentation activator
at 25°C. Both come from two continuous storage tanks with a residence time of 10 hours.
With SSCF, in order to obtain desirable product in concentration and conversion, residence time for
substrates and medium inside the bioreactor should be regarded. In this case the reference time is 5
days that determines vessel volume and other parameters. Another reference time that we have taken
into account from [3] for bioreactor was 7 days, which did not alter the rate of production.
The table below outlines the bioreactor features.
Working V Material Number of vessels Gas-Out Liq-Out

Fermented slurry with 3-4
3985.6 m3 SS316 6 CO2
wt% ETOH
SSCF process includes enzymatic hydrolysis of cellulose and hemicellulose; simultaneous fermentation
of resulting hexose and pentose sugars [4] and consist of different chemical and biochemical reactions
which are described by weight base below (all the data comes from an analysis made in SuperPro
Designer).
162 Cellulose +18 Water  180 Glucose (Conversion 79%)

180 Glucose  88 Carbon Dioxide + 92 Ethyl Alcohol (Conversion 95%)
132 Hemicellulose + 18 Water  150 Xylose (Conversion 80%)
150 Xylose  73,33 Carbon Dioxide + 76,67 Ethyl Alcohol (Conversion 70%)
100 Cellulose  10 Soluble Protein +90 Water (Conversion 99%)
10 DAP + 40 Glucose + 50 Soluble Protein  100 Yeast (Conversion 70%)
The Fermented slurry at 35°C is then stored in beer well for four hours, which allows decoupling of
the batch SSCF process and the continuous distillation process.
[3] A. Aden, M. Ruth, K. Ibsen, J. Jechura, K. Neeves, J. Sheehan, and B. Wallace; Lignocellulosic Biomass to Ethanol Process Design
and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydrolysis Current and Futuristic Scenarios. NREL
(National Renewable Energy Laboratory) , 2002
[4] Deepak Kumar and Ganti S. Murthy; Impact of pretreatment and downstream processing technologies on economics and energy in 20
cellulosic ethanol production. OSU (Oregon State University), 2005
Chapter 4 : Distillation
4.1 - Introduction
The purpose of the distillation section of the separation process is to effect the bulk of the binary
ethanol-water mixture separation and increase the concentration of ethanol in the distillate stream
(tops product) to 90% by mass. It results fundamental reaching via distillation this alcohol
concentration, in order to ensure the final ethanol concentration of 99.8% by mass in the exit stream
of the final pervaporation module, ensuring a product within specification. This separation cannot be
achieved solely with standard distillation, due to the existence of a minimum boiling azeotrope:
characteristics of an ethanol-water mixture are an ethanol concentration of 95.5% by mass and a
boiling point of 78.15°C in the vapour-liquid equilibrium.
One option for the separation is to use a benzene to form a ternary azeotrope allowing the ethanol-
water mixture to be separated. However this adds complications including a potential benzene
contamination of the ethanol product and the questionable sustainability of the use of benzene, which
is carcinogenic and highly flammable, it becomes a risk for the environment, plant operators and local
residents near to the facility.
A suitable alternative is to distil the ethanol-water mixture to a point quite close to the azeotrope and
then use pervaporation to complete the dehydration. This method allows a simpler column design and
avoids the use of chemicals such as benzene. This last alternative is the one that we have chosen.
4.2 – Design Procedure

Our distillation section is composed by a beer column used to remove the heavy part from the process
stream and by the real distillation column in which only a small part of “trash” arrives.
4.2.1 - Beer Column

To begin the design process some approximations were made: having not so precise information on
solutes and solids present in the stream leaving the bioreactor (concentration lower than 7% wt), we
have assumed that only water and ethanol were present. Moreover hand calculations on an Excel File
were conducted to find the operating limits of the column, the minimum number of plates and the
minimum reflux. In particular the beer column calculations have been made to optimise the thermal
state of the feed and in this case the condition of the saturated liquid was the most convenient. The
reflux to the top of column is null because the equilibrium composition of the liquid to the first plate is
smaller than the composition of the liquid feed. It follows that a condenser is not needed in the top.
Once this information had been obtained it was used to carry out a preliminary heat and mass balance
for the column at a sensible operating point.
Mass
Mass balances
balances Mass balances
Mass
Mass
= +
balances
Balances
= + = +
= +
(kmol/h) F D W
= + = +
= +
= + Flow Rate 8490 1091,19 7398,8
Composition 0,021 0,16 0,0005
= ∗ = ∗
= ∗
= ∗
G = R +1 ∗ D G = R +1 ∗ D
G = R +1 ∗ D
G = R +1 ∗ D kmol/h =L+ ∗ G G’ L’
= + ∗
= + ∗
= + ∗ Flow ̅= +0 ∗ ( − 1)
1091,19 1091,19 8490
̅ = + ∗ ( − 1) Rate
̅ = + ∗ ( − 1)
̅ = + ∗ ( − 1)
21
First of all in this column the critical sections are only two because the column has only one frustum.
To be able to go into detail, hand calculations were flanked by the use of HYSYS software, but we got
significant discrepancies in the results: from hand calculations the number of real plates obtained is 9,
while in HYSYS is 14, also the dimension of the column changes a lot passing from 2,31m of diameter to
1,5 m in HYSYS. For our process the number of plates chosen is the one of HYSYS so 14, while the
diameter used comes from hand calculations, but taking into account also weeping, flooding and
entrainment it becomes 2,8m. It is noted that for the calculation of real plates in HYSYS, the generic
efficiency of the column obtained by hand was used, and it is equal to 0,45.
Equilibrium Plot
Theoretical Plates Calculation

# tray Liquid Vapor
1 0,16 0,16
1 0,016365 0,16
2 0,016365 0,11222
2 0,01058 0,11222
3 0,01058 0,0576639
3 0,004895 0,0576639
4 0,004895 0,0039921
4 0,0005 0,0039921
According to the fact that the first column is used to eliminate the heavy part from the process
stream, different solutions could be adopted. For example, the beer column could be constructed with
a single plate, but in order to avoid a too high difference in height between the two, we preferred to
design two columns similar in size. In this way we can obtain a very low composition of ethanol (0,0005
mol) in the bottom of the first column, that is precisely what we want, because the aim is to minimize
the losses. Also the quantity of ethanol at the bottom of the second column is very low: 0,0002 mol.
Moreover, for safety reasons it is better to avoid the construction of a too high distillation column and
22
what is generally done when it is necessary to switch from a very low concentration in the entrance to
a very high concentration in the output is just to use two columns instead of only one.
The calculations of the steam in the bottom of the column were made in a conservative way and these
were used to found an approximated exchange area of the reboiler to get the cost of it and of the
entire column.
Summary table:
Feed
Ethanol composition 0,021 mol
Reflux 0
Q factor 1
Bottom of the column
Temperature 99,51°C
Top of the column
Ethanol composition 0,16mol
Temperature 83,87°C for liquid
96,18°C for vapor
Flow rate
Feed 8490 kmol/h
Top 1091,19 kmol/h
Bottom 7398,8 kmol/h
Sizing
Diameter 2,31 m but the one choosen for weeping is 2,8m
Pressure drops on the plate 141 mm
Residence time 3,11s
Total Pressure drops 752 Pa
Efficiency 0,45
Number of plates 9 (hand calculations) and 14 with HYSYS
Height 9,782m
Heat reboiler
Heating fluid (vapour) 13715 KW *
Pressure 5 atm
Temperature 152°C
Flowrate 6,857kg/s
* Q =Vapour flowrate in the column x (latent heat at Tinf + cp at Taverage x ΔT)
23
4.2.2 - Distillation Column

Since the entrance of the distillation column is practically the distillate of the first column, and
relying on the fact that the beer column doesn’t need a condenser, the feed is in the thermal state of
saturated steam. For this reason the Q factor is equal to zero. To plot the equilibrium data three
polynomials were used.
1 Equilibrium Plot
0,95
0,9
0,85 Equilibrio L-VIN
0,8 45°
0,75
0,7 LIQ_VAP2
0,65 Q.LINE
Vapor composition
0,6
R1.2
0,55
0,5 esaurimento
0,45
basso eq
0,4
0,35 Piatti
0,3 Poli. (Equilibrio L-VIN)
0,25
0,2 Poli. (LIQ_VAP2)
0,15 Lineare (R1.2)
0,1
0,05 Lineare (esaurimento)
0 Poli. (basso eq)
0 0,0 0,1 0,1 0,2 0,2 0,3 0,3 0,4 0,4 0,5 0,5 0,6 0,6 0,7 0,7 0,8 0,8 0,9 0,9 1
5 5 5 5 5 5 5 5 5 5
Liquid composition
From the distillation column we want to obtain a composition in the top of 0,8 mol and to get it, the
minimum reflux ratio to be used is equal to 4,43 and so the resulting reflux found is 5,316 (equal to 1,2
times the minimum reflux ratio). Thanks to these quantities we were able to construct the operative
straight lines: both upper and lower.
The temperatures in the bottom and in the top of the column are 99,8°C and 78°C (for liquid and
vapour) respectively.
Mass
Mass balances
balances
Mass balances
Mass
Mass
= +
balances
Balances = +
= +
= + = +
= + kmol/h F D W
= + = ∗
= + Flow Rate 1091,19 218,02 873,17
G = R +1 ∗ D
= ∗ Composition 0,16 0,8 0,0002
= ∗
= ∗ = + ∗
G = R +1 ∗ D
G = R +1 ∗ D ̅= + ∗ ( − 1)
G = R +1 ∗ D kmol/h L G G’ L’
= + ∗
= + ∗ Flow Rate 1161,21 1379,23 288,04 1161,21
= + ∗
̅ = + ∗ ( − 1)
̅ = + ∗ ( − 1)
̅ = + ∗ ( − 1)
24
In this unit there are 4 critical sections, in couples have given two results of different diameter:
3,14m for the top and 1,06 for the bottom. Also in this case, taking into account weeping, we have used
a correction factor and at the end the two diameters chosen are respectively 3,5m and 1,2m.
In this second column the pressure drop between the plates is higher than the one in the beer column,
being 139 mm (using the conservative approach). The residence time runs from 7s to 18,83s..
In this case the efficiency is lower, it is equal to 0,35 and we have found a large gap of discrepancy
between the theoretical number of plates and the real one, being respectively of 11 and 32.
Theoretical Plates Calculation

# tray Liquid Vapor
1 0,8 0,8
1 0,771191 0,8
2 0,771191 0,7757
2 0,7354 0,7757
3 0,7354 0,7456
3 0,6836 0,7456
4 0,6836 0,702
4 0,6002 0,702
5 0,6002 0,6318
5 0,4353 0,6318
6 0,4353 0,493
6 0,146 0,493
7 0,146 0,2495
7 0,03 0,2495
8 0,03 0,1207
8 0,0111 0,1207
9 0,0111 0,0443
9 0,003661 0,0443
10 0,003661 0,01421
10 0,001 0,01421
11 0,001 0,003445
11 0,0002 0,003445
The final height of the column is 21,36 m and the total pressure drop is equal to 1834 Pa.
The distillation column has been implemented in HYSYS placing the efficiency of each plate equal to
0.35, thus obtaining a value of diameter and of plates equal to the results of manual calculations.
Moreover another simulation has been done with SuperPro Designer, which doesn’t give us information
about the number of plates, but the results obtained from the mass balances are comparable to the
ones present in the excel file, and so we can hypothesize that the approximations made during the
hand calculations are satisfactory.
25
Summary table:
Feed
Reflux 5,32
Q factor 0
Bottom of the column
Temperature 99,6°C
Top of the column
Ethanol composition 0,8mol
Temperature 78°C for liquid and for vapor
Flow rate
Feed 1091,19 kmol/h
Top 218 kmol/h
Bottom 873 kmol/h
Sizing
Diameter from 1st to 23rd plate: 3,5 m
from 24th to 32nd: 1,2m
Pressure drops on the plate 139 mm
Residence time From 7s to 18s
Total Pressure drops 1834 Pa
Efficiency 0,35
Number of plates 32 (hand calculations) and 32 with HYSYS
Heght 21,36 m
Heat reboiler
Heating fluid (vapour) 3167 KW *
Pressure 5 atm
Temperature 152°C
Flowrate 1,58kg/s
* Q =Vapour flowrate in the column x (latent heat at Tinf + cp at Taverage x ΔT)
All the data, calculations and plots are present in the excel file “distillation” attached.
26
Chapter 5: Dehydration
5.1 - Introduction
The final part of the production of ethanol is dehydration. The purpose for which the plant is being
built requires that the concentration of ethanol to water is in the ratio of 99.8% to 0.02%, and this
intense concentration of ethanol is not achievable by simple distillation (azeotrope with a boiling point
of 78.15°C), because it leads to an ethanol concentration of only 95.6 vol% (89.5 mol%) . Therefore, an
extra section entitled dehydration is required in the plant.
Dehydration is defined as, ‘the removal of water from an object’, and in the production of ethanol to
be a supplement in petrol, it needs to be a pure alcohol, which is defined as ‘containing no more than 1%
water’.
Different alternatives are possible, and include:
 The use of molecular sieves, such as synthetic zeolite in pellet form to selectively adsorb
water from the 95.6 vol% ethanol solution. The zeolite can be regenerated an unlimited number
of times by drying.
 The use of membranes to separate ethanol and water: since membrane separation is not based
on vapor-liquid equilibriums, and therefore not subject to the limitations of the water–ethanol
azeotrope, the selective permeation of one of the components is possible by using either
hydrophobic membranes (ethanol permeates) or hydrophilic membranes (water permeates).
Molecular sieves are commonly used to produce pure ethanol (>99.5%). Both the investment, the high
tonnage of molecular sieve needed, and the steam consumption are major drawbacks. Hydrophilic
membranes can be a valid alternative, without steam addition and with a minimum electricity power
required to overcome the transmembrane pressure and create the permeate vacuum [1].
5.2 - Adsorption Column and Molecular Sieve

In the literature examined, most of the plants uses a molecular sieve for the dehydration section and
this is also our first option.
A molecular sieve is a material with very small pores of precise and uniform size (3 μm in our study):
these holes are small enough to block large molecules, but allow the passage of the smallest ones. A
molecular zeolite-sieve is polar-hydrophilic in nature and therefore it strongly adsorbs water. The
characteristics of these molecular sieves include fast adsorption speed, frequent regeneration ability,
good crushing resistance and pollution resistance.
The method for regeneration of molecular sieves chosen is purging with a carrier gas (typical in
ethanol dehydration). The column regeneration is performed using superheated dry ethanol, condensed
and returned to the final distillation column. Both columns adsorb and regenerate alternately, and
ensure the uninterrupted continuous production. The recovered heat in the condensers can be used for
preheating. The heat duty of the molecular sieve operation needs to be entirely supplied from the
plant steam boiler.
A simplified flowsheet of a molecular sieve was designed, composed by

 1st Heat exchanger: it increases the temperature of 95% ethanol stream, exploiting the heat
of exiting stream (ethanol 99.8%).
 2nd Heat Exchanger: it superheats the 95% of ethanol to 120°C, this is a temperature enough
high to avoid the condensation of the mixture inside the adsorption towers. The 1 st heat
exchanger can't provide enough heat to this purpose;
 2 adsorption towers: they adsorb water, changing the mass concentration from 95% to 99.8%.
 Vacuum pump: it is needed to reach a P=50kPa in the column when the desorbing occurs;
 Condenser: its job is to deliver ethanol at the final temperature of 31°C.
[1] Hydrophilic membranes to replace molecular sieves in dewatering the bio-ethanol/water azeotropic mixture; Kang, Huybrecths, Van der
Bruggen; 2014
27
5.2.1- Design of Adsorption Towers and Molecular Sieve

An adsorption times per each tower is taken from [2] and it is about 24 min. In the first 6 minutes it
is required to deviate 40% of the exiting ethanol to the other tower for its desorption.
Several mass balances for these 2 different periods were made and are available in excel file
"Molecular Sieve".
It is considered that only water can be adsorbed and desorbed inside the molecular sieve (mole
fraction accumulated = 1), while ethanol flows out entirely. A final mass balance, for an entire cycle, is
also done to have an average flow rate in the exiting stream.
The sizing of the adsorption bed was completed using equations and guidelines given by [3] and
ZEOCHEM (a manufacturer of the molecular sieve used in the design of the adsorption column).
The diameter of the column should be as small as possible to improve the turbulence and the mass
transfer characteristic, which depends on the film resistance to mass and energy transfer.
[4] provides an expression for the maximum gas velocity before it erodes 1/8" beads.
A theoretical height of the column was just possible to calculate [5]. A correction factor calculation
was available but for lack of time it can't be done. A personal correction factor, considering literature
and similar projects is 50% more.
The following table reassume the design of adsorption column
Adsorption Column
Flow rate IN avg 223 Kmol/h
Flow rate OUT avg 179 Kmol/h
Accumulate Rate max 43,70 Kmol/h
Diameter of the column 0,97 m
Adsorption cycle duration 24 minutes
Desorption cycle duration 6 minutes
Molecular Sieve ZEOCHEM® Z3-03
Type 3A zeolite
LES (Theorical Height of Bed) 4,70 m
Height of Column 7 m
5.2.2 - Design of Vacuum Pump

A vacuum pump is necessary in the desorption step of the molecular sieve. It is designed as a
compressor with an outlet pressure of 101,3 kPa, a service temperature of 120°C and the energy
required is calculated as an isoentropic compression with an efficiency of the 75%. The purpose of the
pump is to reach a pressure of 50kPa [2] which is proper for the desorption of water.
The type of vacuum pump chosen is "Liquid Ring Pump": usually with EtOH-H2O mixture for the
lubricant within the pump it is possible and common to be washed away, causing premature failure.
Rather than using a lubricant, liquid ring vacuum pumps eliminate any metal avoiding metal contact and
reducing the chance of failure [6].
5.3 – Continuous Pervaporation

A definition of the process is provided by Yeom et al., (1996) and Chang et al., (1998), ‘pervaporation is
a membrane process used for the separation of liquid mixtures by means of partial vaporization across
a perm-selective membrane. The permeate is then obtained as a liquid by condensation. The driving
force for permeation is established by maintaining a difference in partial pressure of the permeate
[2]Design of an Ethanol Dehydration System; Hiltz Taylor Baier, 2008
[3] Henley, Ernest J.; Seader, J. D. Separation Process Principles. 2nd Ed. . John Wiley & Sons: New York, 2006.
[4] ZEOCHEM Homepage. Zeochem. September 2007 – April 2008. <http:/www.zeochem.com>.
[5] Perry, Robert H.; Green, Don W. Perry’s Chemical Engineer’s Handbook. 7th Ed. McGraw – Hill: New York, 1997.
[6] Aliasso, Joe. How to Size Liquid Ring Vacuum Pumps. Pumps and Systems Magazine. 2003 28
across the membrane. This is accomplished in vacuum pervaporation by lowering the total pressure on
the downstream side of the membrane.
This process consumes very little energy, operates best with low impurities in the feed and is better
for larger capacities. Feed is preheated and passes continuously through a series of membrane
separation modules, which are located in a vacuum chamber. Permeate is then condensed. A vacuum
pump removes the incondensable from the system.
Advantages:
 Pervaporation is an energy efficient combination of membrane permeating and evaporation, it
involves low temperatures and pressures.
 With this process the capital costs, relative to conventional systems, are reduced.
 The modular membrane design leads to the use of few components and if a particular part is
damaged, it can be easily replaced.
5.3.1 - Membrane selection

For the purpose of the pervaporation module in the bio-ethanol plant, it is necessary to remove the
water, so hydrophilic membranes need to be used.
The membranes are often made of polymers and they are used for two reasons, as suggested by G.H.
Koops and C.A. Smolders:
 firstly, membranes separate a mixture because of a difference in size of the two components.
These membranes show only good selectivity for mixtures with dissimilar steric factors:
components with large steric factors diffuse less quickly.
 secondly, membranes discriminate components thanks to the interaction that is created during
diffusion between one of the separating components and the membrane, as it has been seen
with ion-exchange and hydrophilic membranes. A good hydrophilic compound to use for this
procedure would be polyvinyl alcohol [8].
5.3.2 - Design of Pervaporation Unit

The flow-sheet of the pervaporation unit is very similar to the one of the molecular sieve, already
seen; in this case we use 10 modulus with an exchange area of 326m 2 each. For the heat exchangers of
course temperature parameters change, mainly because the pervaporation unit work at lower
temperature than molecular sieve ( 90°C against 120°C).
The pervaporation unit is arranged in analogy with a heat exchanger; the overall unit will be
rectangular in shape, it will be easy to construct and it will be easier to place the membrane tubes
inside, those pipes are made of PVA and with the shell-side maintained at vacuum pressure.
A reference company manufacturer of pervaporation unit was considered: Kuhni, a Swiss based
company, and in fact some geometry parameters were chosen considering its standards.
The tubes are arranged in a square format: the use of a triangular pitch is not necessary, since that
often helps when cleaning is needed, but here the fluids used are very clean.
Pervaporation Unit Sizing

Material PVA Area of Membrane 326 m2
Temperature Service 90°C Number of Tubes 442
Pressure out 50mbar Tube Length 6m
Temperature Loss 16,5°C Tube Diameter INT-EST 0,10-0,11 m
Permeation rate 0,25 kg/hm2 Tube format-pitch Square – 0,121m
Width x Height 5x5m
The design of pervaporation unit and condenser unit are in the excel file “Pervaporation”.
29
Chapter 6 : Wastewater Treatment
The remaining liquid after distillation of alcohol is the major part of the plant’s wastewater, which
contains non or low volatile fractions of materials. Its composition depends greatly on the type of
feedstock. It generally contains residual sugars (non fermentable sugars), traces of ethanol, other
metabolites produced during fermentation such as glycerol, inhibitors produced during hydrolysis,
waxes, fats and mineral salts. In the actual process, the liquid stream must be partially recirculated to
minimize the requirement for fresh water and the production of wastewater. However, the
consequence of recirculation is an accumulation of inert materials and of inhibitory compounds for the
cellulase enzymes and/or fermenting microorganisms in the process. The degree of recirculation
depends on the process conditions: 40-75% of the streams might be safe to be recirculated to the
process.
Since there is no large-scale process based on the enzymatic hydrolysis for ethanol from
lignocellulosic materials, we should still rely on the results from pilot plants while discussing the
wastewater. Generally speaking, the characteristics of stillage from cellulosic materials might be
comparable with those of conventional feedstocks and, therefore, methods of stillage treatment and
utilization applied to conventional feedstocks might also be applicable to cellulosic feedstocks.
Two possible exceptions to the similarity of cellulosic and conventional stillage characteristics deserve
attention:
 The potential for higher levels of heavy metals from the acid pretreatment equipment;
 The presence of inhibitors, such as hardwood extractives, associated with phenolic
compounds present in the feedstock.
The non-circulated stillage and other wastewater in the plant, could be concentrated by evaporation.
The concentrated wastewater could be incinerated or neutralized with alkali, followed by incorporation
into some special application such as road-building materials. Similar to other substrate stillage, the
stillage of lignocellulosic material may be used for production of potentially viable biological products
including enzymes, chitosan, astaxanthin and single cell protein. Anaerobic digestion, made with
acetogenic and methanogenic bacteria, can be used as an effective process for removing COD from
stillage and converting it to biogas, which is a readily usable fuel for the ethanol facilities. Nowadays a
lot of interesting studies are performed on wastewater treatment, in fact different types of
microorganisms could be used, even the protozoa, which can create diseases to the human health.
6.1 - In the process

In the downstream process the bottom effluent of beer column is passed through a pneumapress filter
that separates it into two streams: a solid stream which contains most of the lignin and a liquid stream
containing most of the water and soluble solids. The lignin rich solid stream is combusted in fluidized
bed combustor for steam generation and it contains about 50% moisture. The liquid stream is divided
into two parts, one fraction (25%) liquid stream is treated in waste water treatment plant and,
remaining liquid, is concentrated in a flash where a pump increases the pressure to 2 bar and then a
valve guarantees the pressure drop till atmospheric pressure. The condensate stream from evaporator
containing water (> 99%) is recycled back as process water. The concentrated syrup after evaporation,
containing about 40% (wet basis) solids is fed to combustor together with the sludge from waste
water treatment. This stream (mixture of lignin stream, evaporator concentrates and sludge) with
about 55% moisture is burned in fluidized bed combustors to produce process steam. In general steam
produced from lignin fraction is more than the steam requirement of plant, so the excess steam can be
used to generate electricity.
The waste water treatment system consists of anaerobic digestion followed by aerobic digestion. The
liquid stream is treated in anaerobic digester using mesophilic bacteria for 10 days, which convert
volatile solids to mixture of methane and carbon dioxide (biogas). Biogas produced from anaerobic
30
digester is burned in the combustor along with lignin residue stream to produce steam. The amount of
biogas generated was calculated on the basis of Chemical Oxygen Demand (COD).
Treated water containing sludge, residues and water is subsequently fed to aerobic digester, with a
residence time of 6 days. The sludge from aerobic digester is fed to combustor as described earlier.
But let’s go in deep in this process.
6.1.1 - COD calculator

In this equipment the stream reacts continuously at 35,09°C under adiabatic conditions in order to get
the value of the COD equivalent. The main reactions can be represented as follows:
1 Glucose + 0,07 water  1,07 CODeq
0,07 Water + 1 Xylose  1,07 CODeq
1 Furfural + 0,67 Water  1,67 CODeq
1 HMF + 0,52 Water  1,52 CODeq
1 Cellulase + 0,45 Water  1,45 CODeq
1 Protein-soluble + 0,45 Water  1,45 CODeq
1 Ethyl Alcohol + 1,09 Water  2,09 CODeq
1 Cellulose + 0,19 Water  1,19 CODeq
1 Hemicellulose + 0,21 Water  1,21 CODeq
1 Soluble Lignin + 1,65 Water  2,65 CODeq
1 Soluble Extractives + 0,07 Water  1,07 CODeq
1 Extractive + 0,07 Water  1,07 CODeq
6.1.2 – Anaerobic Digestor

In the anaerobic digestor reactions take place to biodegrade the CODeq, with a working to vessel
volume ratio of 90% at 35,09°C.
The main reaction can be represented as follows:
1 COD eq  0,22 CO2 + 0,24 CH4 + 0,03 Sludge + 0,51 H2O
6.1.3 - COD calculator

In the second COD calculator the stream reacts continuously at 35,10°C under adiabatic conditions in
order to get the value of the COD equivalent. The reactions are the same made in the first COD
calculator.
6.1.4 - Aerobic Bioxidation Unit

This unit is used to biodegrade under oxygen conditions the remaining COD, with a working to vessel
volume ratio of 90% under adiabatic conditions. Diffused aeration is utilized at a specific rate of
0,07 m3/m3 · min.
The main reaction can be represented as follows:
1 COD eq  0,24 CO2 + 0,30 Sludge + 0,46 H2O
6.1.5 - Belt Filtration

The belt filtration is adopted to transform the sludge to a final solid concentration of 30% wt. The
specific sludge loading rate is 300 kg dry solids/m ·h. Then part of the stream is sent to a fluidize bad
reactor, the other percentage becomes effluent water.
31
Chapter 7 : Economics, Sustainability, Health & Safety
7.1 – Economic Evaluation

In order to assess the economic viability of this project it is necessary to analyse the capital cost, the
operative cost and the NPV of the plant. The NPV, namely the Net Present Value, is the gain that we
will have in 30 years discounted at the value of the dollar today.
7.1.1 – Assumptions:
For this analysis we have made some assumptions:
 A life of the plant of 30 years;
 A discount rate calculated with NREL value of 0,10.
 A selling price of ethanol of 0,70$/L (this value was found with some researches, it is already
on the market and we have used it for some comparisons).
Several methods and databases have been used:

 Guthrie Method for the purchase cost of tanks, vessels, pumps, heat exchangers and
compressors;
 Lang factors for the final instalment cost;
 MATCHE data bases for some equipment units;
 Murthy’s SuperPro Designer File for the units not found in the previous data base;
 Values coming from NREL (National Renewable Energy Laboratory) for the final instalment
costs of equipments for which we haven’t found other information.
A lot of row materials and utilities are bought outside of the plant, such as enzymes, yeasts, grass
straw, sulfuric acid, lime, steam and electric energy, The products that we are able to separate during
the process as yeasts, lignin and biogas, were not considered for a possible sale.
Taxes used for the economic evaluation are those of the United States and are therefore equal to
30% of the annual cash inlet.
7.1.2 - Molecular Sieve VS Pervaporation Unit

For the economical analysis the molecular sieve was evaluated as if it was an absorption column, in
which the filling is made with zeolites (not having found the correction factor for the zeolite, we have
assumed that it could be comparable to that of alumina, and then a correction factor equal 12 was
used) and here the Guthrie method was adopted. The pervaporation was evaluated as if it was a heat
exchanger and so its exchange area was considered for the economic evaluation, the Guthrie method
was adopted with a correction factor of 4.
At the end the result is that the most expensive unit between the two is the molecular sieve: it is
composed by two units of 500 000$ each (total 1 000 000$), instead the pervaporation unit has 10
modules of 45 000$ each (in total 450 000$).
Starting from the fact that if we want to see the changes from the economical point of view of the
pervaporation unit and of the molecular sieve, it is useless to do it all over the scale of the system, we
focused our attention on what we have developed in HYSYS. Obviously the cost of the equipment up to
the second column remains unchanged, while from the reboiler and the condenser of the second column
to the downstream (until the final stream of pure ethanol) these costs are different. The results
obtained have allowed us to compare these two techniques: the molecular sieve has a total cost of 42
millions dollar while the pervaporation unit of 27 millions dollar, both implemented in 2014.
All costs were calculated by American lease (Oregon) and so it was not necessary to do the conversion
of currency.
32
With these results the total cost of the plant is found to be: 89 millions of dollar for the molecular
sieve and 70 millions for the pervaporation unit.
7.1.3 - NPV calculation

As it is indicated in [1] the working capital is about 10% of the fixed capital investment, in our case for
molecular sieve is 8,9 millions dollar, instead for the pervaporation unit is 7 millions dollar. One month’s
raw materials, labor and utilities is 3,35 millions dollar therefore a lower number seems reasonable. [1]
suggests that using a fraction of the yearly operating cost typically 10% is more relevant, in our case
at the end it is 4 millions dollar.
Another calculation was developed using the slides given to us by the Professor Tugnoli, in order to
obtain the total operating costs, choosing a final income equal to 1.3 of the total costs of operation.
From here we have calculated the cost per liter of ethanol that for the Molecular Sieve is 2.95$/L and
for the pervaporation unit is 2.47$/L (both very different from the selling price found).
At this point the NPV was calculated following 3 different pathways:
 according to the slides of Professor Tugnoli, maintaining a cost of sales per liter of ethanol
equal the one calculated as 1.3 times the operating costs, in this case it is 2.24·108$.
 wanting to be more competitive we calculated the NPV with the same method explained before,
but with a selling price for ethanol of 0.7$ / L; in this case the final NPV is -6.24· 108$.
 with revenues calculated from [1] and with a cost for ethanol of 0.7 $/L the final NPV is
1.99· 107$.
All these amounts are related to the pervaporation, but the same pathways have been followed also for
the molecular sieve, getting:
 NPV1 = 2,62· 108$
 NPV2 =-9 ·108$
 NPV3= 90 000$ (this has a high discrepancy with the other values because the annual cash
flow is very low)
At the end, from the economic evaluation it is shown that in 30 years we will get a gain of 23 millions
dollar with the pervaporation unit and 900 000 $ with the molecular sieve.
All the calculations and the data for the “Economic Evaluation” are available in the attached
“Economical Analysis” excel file.
7.2 – Sustainability: Environmental Impact Evaluation

In this study, the environmental impact assessment was conducted using CLM2002 (Chain Management
by Life Cycle Assessment) methodology.
The primary objective of the impact assessment stage is to transform the long list of Life Cycle
Inventory results into a limited number of indicator scores. These indicator scores express the
relative severity on an environmental impact category. A midpoint approach was taken: midpoint
methods convert the emissions of hazardous substances into impact category. This provides
information about the amount of input or output of, for example, chemicals or materials from the
product or system that can impact on a particular issue. Within this study the following midpoint
impact categories are analyzed: global warming, photochemical oxidant formation, acidification,
eutrophication, human toxicity and abiotic depletion (fossil and element). Classification and
characterization are applied; weighting and normalization are also considered in this paper. Moreover
the water consumption was taken into account.
[1] Process design and economics for biochemical convertion of lignocellulosic biomass to ethanol, NREL 2011 33
7.2.1 - Goal and scope

The goal of the study is to quantify the environmental impacts of the production of bio-ethanol from
grass straw. In particular the conversion of biomass to ethanol was studied but also production of
materials needed were taken into account, as for example sulfuric acid and enzymes. About the
production of grass straw it was calculated its environmental impact but not the CO 2 sequestration
during its harvesting. Moreover a comparison between the environmental analysis of the molecular
sieve and of the pervaporation unit has been done.
7.2.2- Functional unit

The functional unit chosen to compare the environmental assessment is 1 h of plant's production of
ethanol from grass straw. Considering the base case, the one where the dehydration is obtained with
the molecular sieve, this is equivalent to a production of 8317 kg of ethanol or 224,5 GJ of energy
available (considering a Low Heating Value of ethanol =27 MJ/kg), while in the case of pervaporation
the value is higher.
7.2.3 - System boundary and data source

The system boundary analyzed is composed by the entire ethanol conversion plant, the production and
transportation of the following materials: sulfuric acid, limestone, cellulase and biomass. What is
missing is the production of yeast, but it can said that extraction of yeast after the bioreactors is
sufficient to provide the amount required for fermentation, so it can be assume that there is no
production of yeast assuming a null balance.
The data considered for materials production comes from the GREET 2014 software (The Greenhouse
Gases, Regulated Emissions, and Energy Use in Transportation Model) . Instead the indirect emissions
derived from energy consumption refers to ELCD Italy power grid mix, due to the absence of certain
US data.
The data of grass straw indirect emissions were not found, but a reasonable approximation was taken:
instead of tall fescue data it has been used the switchgrass's data from GREET. As it is a kind of
plant similar to tall fescue, these data can be representative of an average value, valid also for tall
fescue.
7.2.4- Results
As it can be seen in the plot the categories most dangerous are Global Warming (emissions to produce
the electrical energy and emissions from the bioreactors are very relevant) and Acidification (mainly
caused by the presence of sulfuric acid which can't be removed in the centrifugation and of course
also by the presence of SOx in the energy production from fossil fuels). About Photochemical
Oxidation the biggest contribution is given by fugitive emissions of ethanol along all the ethanol
conversion plant.
Water consumption is not present between the categories of CML2002 but anyway it was estimated
because it's an interesting parameter. It results that the ethanol conversion plant required 1306
tons/h of water if molecular sieve is used and 989 tons/h of water if pervaporation unit is applied, it is
a high value, but in general the plant for the production of bio-ethanol requires a huge amount of
water, more than the one necessary in the conventional ethanol production plant. Half of this amount is
needed to maintain cool the bioreactors, which must be at 35°C to allow the reaction inside it and to
avoid the death of Saccharomyces cerevisiae . Other units that need water are in the pervaporation:
the rectification column and the condenser.
The GhG emissions are 34000 kg of CO2eq, generally the value obtained is negative, because during its
life the grass straw takes CO2 from the environment and the one produced in the process remains
lower than this value. Unfortunately the available data were not sufficient to consider the CO2
sequestered for its growth, so it wasn’t taken into account for the Environmental Analysis.
All the calculations and the data for the Environmental Impact Evaluation are available in the
attached “Environmental Analysis” excel file.
34
Environmental Impact Evaluation

9,00E-006
8,00E-006
7,00E-006
Normalized Indicators
6,00E-006
5,00E-006
4,00E-006
3,00E-006
2,00E-006
1,00E-006
0,00E+000
Abiotic Resources Global Warming Human Toxicity Acidification PhotoChemical Oxidation Eutrophication
7.2.5 - Molecular Sieve VS Pervaporation

The environmental evaluation of different technologies available for dehydration section leads to the
same value of categories index. An aggregated index, after weighting the categories, was calculated:
it's equal to 4,96 ·10-6 for the molecular sieve and to 4,93 ·10-6 for the pervaporation unit.
Indeed, the main difference is the absence of recirculation to the rectification column when
pervaporation modules are used. That flowrate doesn't change so much the bottom stream of the
column. Further, the two technologies analyzed doesn’t emit any substance directly. A little variation is
due to the different energy requirement: the pervaporation needs less energy (120 kW against 250
kW) because in the molecular sieve we have used a compressor to set the pressure at 250kPa. The use
of the compressor causes a loss of energy gained from the vacuum pump. In this study it was assumed
that inside the pervaporation unit and in the molecular sieve no ethanol is lost so the water absorbed is
pure. This is of course not real and must be considered in pervaporation where this stream goes
directly to wastewater treatment: this means that a bigger amount of ethanol is emitted in the
effluent water, but we didn’t calculate this value for an easier mass balance.
The different equipment used also influenced the calculation of fugitive emission. In particular the
presence of the recirculation leads to a higher number of valves, splitters and mixers, that causes in
the molecular sieve a bigger amount of fugitive emissions.
Allocation is applied: energy balance was made to evaluate how much steam can be produced from lignin
and methane. It was found that sufficient energy is available to cover the steam demand of the entire
ethanol plant conversion. It was also possible to generate a little bit of electricity maybe using a
turbine but it was not considered relevant so this consideration was omitted. At the end we simply
declare that no energy is required for steam production.
7.3 – Health & Safety

7.3.1 - Information on Safety
The primary piece of legislation to be adhered to is the Health and Safety at Work Act (1974). This
sets out the responsibilities of the employer to the employee, in essence; “It shall be the duty of
every employer to ensure, so far as is reasonably practicable, the health, safety and welfare at
work of all his employees.”. This can be embodied, in an industrial environment, through properly
outlined working procedures and active health and safety monitoring, often coordinated by a dedicated
site SHE (Safety, Health and Environment) manager.
7.3.2 - Operational safety

To ensure the safety of the plant operatives several procedures (both on a design and operational
level) can be used to both raise awareness of safe working practises and monitor safety performance.
- MSDS (Material Safety Data Sheets) should exist for every chemical used on site and
operators should be aware of the information. For example boiler house energy controllers
35
should be aware of the dangers presented by the various water treatment chemicals used,
ranging from brine to sulphuric acid.
- Correct PPE (Personal Protective Equipment) should be worn at all times, initiatives should be in
place to inform workers of requirements, this can be as simple as signposting mandatory high-
visibility areas.
- All chemical storage tanks should be properly bounded to prevent loss of containment from
occurring and putting employees and the environment at risk.
- Ethanol Storage tanks should be positioned away from main plant items and sufficiently spaced
to minimise the risk fire spreading.
7.3.3 – Sulfuric Acid

Having a pre-treatment made with a dilute acid, and in particular the one used is Sulfuric Acid, we
have to take into account also its characteristics. Even if it is used diluted, we store it pure, so some
considerations have to be done: it is not flammable and not explosive, but it is corrosive and reacts
violently with water. For these reasons several precautions have to be taken: first in case of dilution
with water (as in our case) it is important to add the acid with the water, the inverse operation must
be avoided; then it is important to use gloves, mask, glasses and a protective suit.
According to the non flammable and non explosive properties of Sulfuric Acid we have focused our
attention on the characteristics of Ethanol, definitely more hazardous.
7.3.4 – Ethanol
IUPAC NAME Ethanol

COMMON NAME Ethylic Alcohol
GENERAL CHARACTERISTICS
MOLECULAR FORMULA C2 H 6 O
MOLECULAR MASS 46,07 u
ASPECT Uncoloured liquid
CAS NUMBER [64-17-5]
CHEMICAL-PHYSICAL PROPERTY
DENSITY 0,789
REFRACTION INDEX 1,3611
(293 K, 589 nm)
FUSION TEMPERATURE −114.3 °C (158,8 K)
ΔfusH0 4,9 kJ·mol−1
ΔfusS0 31 J·K−1mol−1
BOILING TEMPERATURE 78.4 °C (351,5 K)
Δeb H0 38,56 kJ·mol−1
SECURITY INFORMATION
FLASH POINT TEMPERATURE 12,7 °C (286 K)
AUTOIGNITION TEMPERATURE 425°C (698 K)
SECURITY CLASS IB (easily flammable)
From MSDS (Material Safety Data Sheets) the threshold limit value of pure ethanol was found to be
1000ppm. Although ethanol is a non-reactive substance (Nr=0), it is very explosive and flammable
(Nf=3) with the lower and upper flammable limits of 3.3 % and 19% respectively. It also has a very low
flash point of 12,7 °C or 55 °F. On the basis of a exposure time of four hours, the acute oral toxicity
(LD50) of ethanol was found to be 3450 kg/mg and the acute toxicity of the vapour (LC50) of ethanol
was found to be 39000 m3/mg . This classifies ethanol to be slightly hazardous in the case of ingestion
or inhalation. It is also an irritant in the case of skin contact.
36
Personal protective equipment such as protective gloves, safety goggles, and fire retardant clothing
are recommended whenever working with or near ethanol.
Concentrated ethanol solutions should be stored in a tightly closed and sealed container in a cool well
ventilated area that will not exceed a temperature of 23 °C.
Proper ventilation and accessible eye wash stations and dry chemical fire extinguishers are also
necessary.
7.3.5 - DOW Fire and Explosion Index Analysis

A Fire and Explosion Index analysis was made on the distillation column, because it represents the
most hazardous unit, on the molecular sieve and on the pre-evaporation unit in order to make a
comparison between these two. The analysis was made following the Dow’s Fire and Explosion Index
Hazard and Classification Guide, in which the Material Factor is obtained at ambient temperature, for
this reason the flammability signal (Nf) and the reactivity signal (Nr) have been adjusted: the MF used
is not 16, but 21 thanks to the correction.
The F&EI Analysis for all the three operation units are attached to this report in the “FEI
Safety” excel file. Remembering that a F&EI between 1 and 60 means light hazard, between 61 and
96 means moderate, between 97 and 127 means intermediate, between 128 and 158 means high and
higher than 159 means very high, we get:
 A F&EI of 214,83 was obtained for the distillation column = very high hazard!
 A F&EI of 96,6 was obtained for the molecular sieve = intermediate hazard!
 A F&EI of 88,2 was obtained for the pre-evaporation unit = moderate hazard!
The safety evaluation of the two different technologies available for dehydration section leads to a
result that we expected: a higher risk for the molecular sieve, due to the fact that the inlet stream is
a vapor. Obviously the most dangerous unit remains the column because both the temperature and the
quantity of ethanol are high.
7.3.6 - HAZOP
A HAZOP (HAZard and Operability) study
provides a framework for assessing a whole
production plant one major plant item at a time.
This allows for potential hazards arising from
operation that has deviated from design point
to be found and a plant profile created. The
study can improve not only safety but also
operational productivity, carrying out HAZOP
at the design stage allows potential hazards to
be rectified before construction has begun,
reducing capital investment. The HAZOP study
wasn’t the goal of our safety
analysis so we propose only an example made on the distillation column, but obviously similar analysis is
appreciable to the other main processes: pretreatment, hydrolysis, fermentation, etc…
The figure shows a schematic of the distillation column showing flows and pumps, a HAZOP analysis has
been conducted for this plant item using the guide words MORE, LESS and NO, two potential hazards
have been identified under each keyword.
37
Deviation MORE - steam to reboiler Deviation MORE-distillate flow

Cause Valve or control system failure Cause Control system failure, increased
demand
Consequences Large vapour flow in column Consequences Increased condenser heat load, not all
distillate condensed
Hazards Hazards Liquid entrainment and Hazards Column overheating
column flooding
Deviation LESS-steam to reboiler Deviation Column overheating

Cause Valve or control system failure Cause Valve, pump or control system failure
Consequences Reduced vapour flow in column Consequences Inadequate rectifying
Hazards Condensation of vapour forming Hazards Off spec product can affect processes
vacuum downstream
Deviation NO-feed to Column Deviation NO-bottoms flow

Cause Pump failure Cause Pump failure
Consequences Less liquid in column Consequences More liquid in column, no feed preheat
Hazards Reboiler overheating Hazards Reboiler overheating, column flooding
As can be seen three of the hazards identified are triggered caused by the failure of a pump. This allows
for backup pumps to be incorporated into the design of the column and its control system, ensuring
continuous safe production as possible.
38
Chapter 8 : Conclusions
The report has successfully outlined a proposal for a bio-ethanol production plant with a capacity of
8,065 tonnes of ethanol per hour if the pervaporation is used, or 8,037 tonnes of ethanol per hour if
the molecular sieve is used, at a purity of 99.8%, using grass straw (tall fescue) as the feedstock.
A potential location for the production plant would be Willamette Valley in Oregon: it covers about
500,000 acres under grass seed production, in fact in Oregon, about 0.88 million metric tons/year of
grass straw is available as a co-product from grass seed production.
Such a project can bring many benefits to the local area including employment and training
opportunities as well as a boost to the local economy. However it is important that support is
generated and key allies made such as the fuel retailers and more importantly the local residents.
The fuel produced by the plant will have a positive effect on climate change. The energy released from
burning the fuel is significantly less than that required to produce it. Ethanol fuel blends will help
improve air quality by reducing the emissions of components of smog and harmful additives.
An economic analysis has shown this product to be viable under a number of market conditions; high
and low government tax, oil prices and feedstock costs. The product will yield large profits with the
current government subsidy on bio-ethanol fuel tax, and a cash-flow analysis shows that the pay back
period would be 29 years from project initiation under these conditions.
At the end, from the economic evaluation it is shown that in 30 years we will get a gain of 23 millions
dollar with the pervaporation unit and 900 000 $ with the molecular sieve.
Considering its benefits, this plant is an environmentally viable means for producing bio-ethanol for the
US market. Further development of this proposal would be necessary to construct a fully integrated
flow-sheet using a commercial software package and carry out a detailed analysis of resource use, with
a view to maximising resource efficiency.
From our study of the comparison between the molecular sieve and the pervaporation unit has emerged
as from a point of view of the environmental analysis there are no substantial differences, from a
point of view of safety is better the pervaporation and from an economic point of view the best is the
pervaporation unit.
From our study of comparison between the molecular sieve and the pervaporation unit has emerged as
follows:
 from a point of view of the environmental analysis there are no substantial differences: the
dehydration is not a critical section of the system and so the two technologies do not affect
the impact of the total emissions;
 from a point of view of safety is better the pervaporation: from F&EI Analysis we have
obtained, as we expected, the highest hazard in the distillation column, and doing the
comparison between the molecular sieve and the pervaporation technologies not a so relevant
distinction appears, even if the two hazards are part of 2 different categories of risk
(intermediate and moderate), they are at the border lines of the distinction;
 from an economic point of view the best is the pervaporation unit: although neither option is
really convenient in economic terms, the pervaporation is better. The gain is there but the
investment is too high so future efforts should focus on lowering capital investment.
39
Flow-sheets (Molecular Sieve)

In SuperPro Designer
In HYSYS:
40
Flow-sheets (Pervaporation Unit)

In SuperPro Designer
In HYSYS:
41
Bibliography
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mixture; Kang, Huybrecths, Van der Bruggen; 2014
Design of an Ethanol Dehydration System; Hiltz Taylor Baier, 2008
Henley, Ernest J.; Seader, J. D. Separation Process Principles. 2nd Ed. . John Wiley & Sons: New York,
2006.
ZEOCHEM Homepage. Zeochem. September 2007 – April 2008. <http:/www.zeochem.com>.
Perry, Robert H.; Green, Don W. Perry’s Chemical Engineer’s Handbook. 7th Ed. McGraw – Hill: New
York, 1997.
Aliasso, Joe. How to Size Liquid Ring Vacuum Pumps. Pumps and Systems Magazine. 2003
Negri di Montenegro, Peretto; Sistemi Energetici e Macchine a Fluido 1, 2009
Design Proposal: Bioethanol Production Plant, Braisher, Sanampreet, Treharne, 2006
Manufacturer KUHNI standard , www.sulzer.com
Graeme M.Walker; Bioethanol: Science and technology of fuel alcohol; Ventus Publishing Aps, 2010
TMO: Converting Low value waste into high value energy; www.tmo-group.com
A. Aden, M. Ruth, K. Ibsen, J. Jechura, K. Neeves, J. Sheehan, and B. Wallace; Lignocellulosic Biomass
to Ethanol Process Design and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic
Hydrolysis Current and Futuristic Scenarios. NREL (National Renewable Energy Laboratory) , 2002
Deepak Kumar and Ganti S. Murthy; Impact of pretreatment and downstream processing technologies
on economics and energy in cellulosic ethanol production. OSU (Oregon State University), 2005
Mohammad J. Taherzadeh and Keikhosro Karimi; Enzyme-based Hydrolysis Processes for ethanol from
lignocellulosic materials, ncsu.edu/BioResources, 2007
A. Aden, M. Ruth, K. Ibsen, J. Jechura, K. Neeves, J. Sheehan, and B. Wallace; Lignocellulosic Biomass
to Ethanol Process Design and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic
Hydrolysis for Corn Stover. NREL (National Renewable Energy Laboratory) , 2002
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Biofuels, 2011
EPCON Evaporation technology AS, Flash Cooler: Concentration and Instant Cooling, 2003
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Chemical Engineering University of Saskatchewan, 2007
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Ethanol Production in the Pacific Northwest US, NREL (National Renewable Energy Laboratory) , 2011
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demonstration facilities in June 2010, IEA BIOENERGY TASK 39, 2010
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43
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Bioethanol production plant - pretreatment with diluted acid

Technical Report · January 2015

Gheorghe Falca Sahand Iman Shayan

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Goal: Preliminary design and performance analysis of a section of a cellulosic ethanol

Biomass Grass straw

Output (ethanol) specification:

Chapter 3 : Hydrolysis and Fermentation

Chapter 6 : Wastewater Treatment

Chapter 7 : Economics, Sustainability, Health & Safety

1.2 – Second generation bio-fuels

Bio-fuels Energy Balance Energy Balance

1.3 - Bio-ethanol as a fuel

1.4 - The production of Bio-ethanol

1.5 – Different pre-treatments

1.6 – Location of Plant

1.7 – Grass Straw Composition

2.1 – Heterogeneity of the starting raw materials

Among them are worth mentioning:

2.2 – Lignocellulosic raw materials

2.3 – Diluted acid pre-treatment

2.4 – The process

Collection in 2 phases: The mechanical collection takes

Discharge of the sheared

2.4.1 – The conveyor belt

2.4.2 – The Straw Storage

2.4.3 – Mixing with recycle

2.4.4 – Washing (Bulk Flow)

2.4.5 – Flow splitter

2.4.7 – Stream Mixing

2.4.8 – Water Mixing

2.4.9 – The Sulfuric Acid Storage

2.4.11 – Fluid Flow Pump

2.4.12 – Heat exchanger

2.4.13 – Pre-treatment reactor

2.4.14 – Solid-Liquid separator

- One between the product just formed and water:

- one to give rise to gypsum:

Chapter 3 : Hydrolysis and Fermentation

3.1 Enzymatic Hydrolysis

3.1.1 Cellulolytic Enzymes

3.1.2 Important Factors in Enzymatic Hydrolysis

Estimated potential glucose =

2) using the enzymatic assay described below

Hydrolysis yield with time for tall fescue

3.2 Hydrolysis and Fermentation Strategies

3.2.2 – Several Microorganisms

3.2.3 – The chosen strategy: SSCF

3.2.4 In the flowsheet

Working V Material Number of vessels Gas-Out Liq-Out

162 Cellulose +18 Water  180 Glucose (Conversion 79%)

4.2 – Design Procedure

4.2.1 - Beer Column

Theoretical Plates Calculation

* Q =Vapour flowrate in the column x (latent heat at Tinf + cp at Taverage x ΔT)