Biobased Chemistry and Technology

Thesis Biobased Chemistry and Technology

Process design of
lignocellulosic biomass
fractionation into cellulose,
hemicellulose and lignin by
prehydrolysis and
organosolv process
Juan Holgueras Ortega

July 2015

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 Lignocellulosic biomass
fractionation into cellulose,
hemicellulose and lignin by
prehydrolysis and ethanol
organosolv treatment

Name course : Thesis project Biobased Chemistry and

Technology
Number : 029BCT
Study load : 24 ects
Date : 15*03*2015/15*07*2015

Student : Juan Holgueras Ortega

Registration number : 900728353070
Study programme : MsC (Chemical Engineering)

Supervisor(s) : Dr. Ir. Ton Van Boxtel, Ir. Edwin Keijsers

Examiners : Dr. Elinor Scott
Group : Biobased Chemistry and Technology
Address : Bornse Weilanden 9
6708 WG Wageningen
the Netherlands
Tel:+31 (317) 48 21 24
Fax: +31 (317) 48 49 57

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 Index
ABSTRACT 4

LIST OF FIGURES 5

LIST OF TABLES 6

1. INTRODUCTION 7

2. DESIGN OF THE PROCESS 12

3. RESULTS 18

4. DISCUSSION 23

5. CONCLUSIONS 27

6. ACKNOWLEDGEMENTS 28

7. REFERENCES 29

8. APPENDIX 32

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ABSTRACT

Lignocellulosic biomass contains polymers of cellulose, hemicellulose and lignin bound

together in a complex structure. The aim of this research is to find an optimized pretreatment
to extract the three main components at the same time using separation steps that don’t
degrade any of the products during the process. A way to avoid the degradation of
hemicellulose during the organosolv process with EtOH/water mixture is doing a
prehydrolysis before, where the hemicellulose is dissolved in the water and then it is not
submitted to the conditions of delignification during the organosolv process. The process was
modelled using SuperPro Designer and, on the contrary to other processes, it included the
downstream process where the products were treated with drum drying and decanters to
obtain as purified as possible the products. The results obtained are very promising and show
high yields for cellulose, hemicellulose and lignin of 80.3%, 54% and 60% respectively, but it
has to be taken into account that there were some assumptions along the process because the
data used was taken from batch processes and not for continuous processes, to reach more
accurate results more experiments should be done in the lab in continuous process. Some
experiments have been done in previous works where it was only studied the reactions where
the components where extracted without taking into account the downstream process, which
means that the products are not separated from the rest of the components and then there are
no losses during the process as in this study.

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 LIST OF FIGURES
Figure 1. Functional block diagram of experiments done in [2] for fractionation of
lignocellulose.

Figure 2. Functional flow diagram of process shown in [2] for fractionation of lignocellulose.

Figure 3. Block diagram of lignocellulosic biomass pretreatment (prehydrolysis followed by

organosolv process).

Figure 4. Fraction of lignin dissolved depending on the organic solvent proportion.

Figure 5. Flowsheet of the fractionation of lignocellulose through prehydrolysis and

organosolv process.

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 LIST OF TABLES
Table 1. Value of kinetics for reactions during the prehydrolysis step.

Table 2. Value of kinetics for reactions during organosolv process.

Table 3. Results obtained in the product stream of xylose.

Table 4. Results obtained in the product stream of cellulose.

Table 5. Results obtained in the product stream of lignin.

Table 6. Amount of chemicals used every year during the extraction process.

Table 7. Annual cost of chemicals used during the extraction process.

Table 8. Power demand in the process.

Table 9. Cost of raw materials per kg used during the process.

Table 10. Executive summary and profitability analysis of extraction process.

Table 11. Data for hydrolysis of three main components of hemicellulose in prehydrolysis and
organosolv process.

Table 12. Energy recovery of the process for operations requiring cooling (Heat sources)

Table 13. Data for recirculation from first flash system (P-7 / V-101) with water stream S-147
(Outlet stream, S-105).

Table 14. Data for recirculation streams from second flash system (P-16 / V-105) and
distillation columns (P-21 / C-101) and (P-23 / C-102)

Table 15. Data for recirculation streams used in the process.

Table 16. Economical evaluation of the process.

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 1. INTRODUCTION
High worldwide demand for energy for the production of transportation fuels, chemicals and
concern over global climate change have led to an increasing interest in the development of
alternative energy and chemicals that can displace fossil transportation fuel [3] [4].

Lignocellulosic materials are one of the most promising feedstock as natural and renewable
resource that can be used in biorefinery. A considerable amount of such materials as waste
by-products are being generated through agricultural practices mainly from various agro
based industries. Recently lignocellulosic biomass have gained increasing research interests
and special importance because of their renewable nature. The huge amounts of
lignocellulosic biomass can potentially be converted into different high value products
including bio-fuels, value added fine chemicals, and cheap energy sources for microbial
fermentation and enzyme production compare to mineral fuels that are fractionated to obtain
different products [5]. It represents a real alternative source of sugars (to replace starch and
sugar agro feedstock), it has high availability/limited competition with food production and
low-cost feedstock [6].

Apart from the three basic chemical compounds lignocellulose contains, water and minor
amounts of proteins, minerals and other components. These components do not participate
significantly in forming the structure of the material. [6].To efficiently use biomass for
biorefinery, it needs to be fractionated into its major constituent cellulose, hemicellulose and
lignin with an average composition of 30%, 45% and 25% respectively.

Inside the lignocellulose complex, cellulose retains the crystalline fibrous structure and it
appears to be the core of the complex, acting as a major structural component of plant cell
walls, which is responsible for mechanical strength [5]. Hemicellulose is positioned both
between the micro and the macro fibrils of cellulose while lignin, which can be found in the
interfibrous area and also in the cell surface [7], provides a structural role in the matrix where
cellulose and hemicellulose are embedded.

Lignin is a polymer made of three types of monomers and is amorphous (non-crystalline). It is

the binder in all plants gluing the cellulose fibers together, it provides physical strength and
forms the secondary wall of cells and plants [8] [9]. It is normally the most complex and
smallest fraction of the biomass. It has a long-chain, heterogeneous polymer composed
largely of phenyl-propane units most commonly linked by ether bonds. It is present in all
plant biomass; therefore, it is considered by-product or as a residue in bio-ethanol production
process [10][11].

Cellulose is more resistant and therefore requires more rigorous treatment, has a long chain of
one type of beads (polymer of glucose), it forms crystals and it has the same chemical
structure in every plant, it is a linear polymeric material consisting of glucose monomers
connected by β-(1-4)-glycosidic linkages, leading to a fibrous and crystalline structure [12]
while hemicellulose has long branched sugar chains, amorphous and it has C6, C5 and C4
sugars [9].

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Unlike cellulose which is homogeneous polysaccharide, hemicellulose is heterogeneous
polysaccharides composed of polymer of pentoses (xylose and arabinose), hexoses (glucose,
galactose and mannose). Xylan is the main component of hemicellulose in grasses and
hardwood, while glucomannan is the dominant hemicellulose component in softwood [12].

Cellulose pulp can be used for paper production or as carbohydrate source for chemicals or
biofuels like bioethanol or bio-butanol. Hemicellulose-derived sugars can be used as a
substrate for fermentation or anaerobic digestion. Alternatively, sugars derived from the
hemicellulose fraction can be (thermo) chemically converted into furfural, which can be used
as a solvent or resin. Lignin is a renewable source of aromatics for a range of chemicals and
can be used as natural binders and adhesives or sub-bituminous coal [13] [14].

Recalcitrance and pretreatments

Biomass conversion is a considerable technique challenge because the cell wall is a
heterogeneous solid composed of carbohydrate fraction tightly interlinked with a complex
alkyl-aromatic fraction which makes the separation of the biomass complicated. There is an
effect because of the biomass recalcitrance, which is the natural resistance of plant cell walls
to microbial and enzymatic deconstruction [15] and makes the separation process have high
cost.

The natural factors [16] that contribute to the recalcitrance of the biomass affect the liquid
penetration and enzyme accessibility are the following ones:

- Relative amount of thick wall tissue.

- Structural heterogeneity and complexity of cell wall constituents such as microfibrils
and matrix polymers.
- Complex structure of the plant cell wall

At the molecular level, the crystalline cellulose of cell-wall micro fibrils is highly resistant to
chemical and biological hydrolysis because of its structure. There are glucose residues in the
cellulose that forces a strong inter chain hydrogen bonding between adjacent chains in a
cellulose chain and weaker hydrophobic interactions between cellulose sheets. This
hydrophobic interactions makes crystalline cellulose resistant to acid hydrolysis because it
contributes to a dense layer of water near the hydrated cellulose surface. The strong inter
chain hydrogen-bonding net-work makes crystalline cellulose resistant to enzymatic
hydrolysis while hemicellulose and amorphous cellulose are readily digestible [4].

Solutions to recalcitrance
The first step in the fractionation of lignocellulosic biomass into fuels or chemicals typically
involves a biomass pretreatment step, which aims at making the cellulose more easily
hydrolyzed by removing the hemicellulose, increasing the surface area and porosity but
reducing the crystallinity of the cellulose [11] . Pretreatment is a crucial process step for the
biochemical conversion of lignocellulosic biomass into bioethanol. It is required to alter the
structure of cellulosic biomass to make cellulose more accessible to the enzymes that convert
the carbohydrate polymers into fermentable sugars [17].

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Pretreatment is still one of the most expensive stages within lignocellulosic biomass
conversion process and there are a large number of possibilities. Minimizing energy, chemical
and water inputs, preserving cellulose and hemicellulose fractions, avoiding size reduction
and limiting formation of inhibitors are key issues to develop cost-effective pretreatment
methods [12]. The most important pretreatments can be seen as follows:

- Mechanical Pretreatment
The reduction of particle size is essential for the fractionation to make material
handling easier and to increase surface/volume ratio. This can be done by chipping,
milling or grinding [18]. It can also be done using the method of ultrasonication which
is a well-known technique for treatment of sludge from waste water treatment plants
[19]
- Chemical Pretreatment

o Liquid hot water (LHW)

The biomass is treated with water at high temperature and pressure [7].
Polysaccharide hydrolysis, can result in the formation of monomeric sugars
that may further decompose to furfural [20]
o Acid hydrolysis
Dilute (mostly sulfuric) acid is sprayed onto the raw material and the mixture
is held at 160-220°C for short periods up to a few minutes [9]. The hydrolysis
of hemicellulose releases monomeric sugars and soluble oligomers from the
cell wall matrix into the hydrolysate. Process with a good performance in terms
of recovering hemicellulose sugars but there are also some drawbacks, but
acids can be corrosive and neutralization results in the formation of solid waste.
This method is good for biomass with low lignin content, as almost no lignin is
removed from the biomass [7].
o Alkaline hydrolysis
It is based on saponification of intermolecular ester bonds crosslinking xylan
hemicelluloses and other compounds such as lignin [7]. It can be done with
calcium or sodium hydroxide, where the addition of air or oxygen to the
reaction mixture greatly improves the delignification, especially highly
lignified materials [21]. The hydrolysis can also be done with ammonia (AFEX)
at elevated temperatures, reducing lignin content and removing some
hemicellulose while decrystallising cellulose.
o Organosolv process
These processes use an organic solvent or mixtures of organic solvents with
water like methanol, ethanol or acetone for removal of lignin before enzymatic
hydrolysis of the fraction. In addition to lignin removal, hemicellulose
hydrolysis occurs leading to improved enzymatic digestibility of the cellulose
fraction [7].

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 o Steam explosion
It is one of the most applied pretreatments because of its low use of chemicals
and limited energy consumption. In this method high-pressure saturated stream
is injected into a batch or continuous reactor filled with biomass. The
temperature rises to 160-260°C, pressure is suddenly reduced and the biomass
undergoes an explosive decompression with hemicellulose degradation and
lignin matrix disruption as [7] [22].
o Ionic liquid pretreatment
Ionic liquids are a mixture of salts that melt at low temperature. Potential
advantages over the methods are the ability of certain ionic liquids to
dissolve/decrystallise cellulose (dissolution process) and/or to extract and
dissolve lignin. Recent studies have shown that these novel solvents possess
interesting properties over molecular organic solvent, such as a negligible
vapor pressure, high conductivity and thermal stability, high conductivity and
thermal stability, high solvating capacity for either polar or nonpolar
compounds [23]. Unfortunately, the recovery of the ionic liquid is still not
fully studied and the costs of the material can be a handicap.

Due to the tight structure of these three polymers, it is very difficult to convert them into bio-
chemicals and biofuels, most recent researches have focused on the fermentation of cellulose
and hemicellulose because of its content in sugars, which can be further converted into
ethanol or butanol and lignin, which can be converted to added value products [7]
However, these researches focus either on the fermentation of cellulose and hemicellulose [7].
The fermentation of glucose, main product of both of them, to ethanol is an already
established and efficient technique [29] . The or extraction of lignin but not on an optimized
pretreatment taking into account the obtaining of the three main components at the same time.
The main question is then: Is it possible to use a pretreatment that can do a fractionation of
lignocellulose that benefits the three main components?
Following the main question, the research information on processing lignocellulosic feedstock
is mainly laboratory work on batch process scale. How is it possible to translate this
knowledge into a large scale continuous process?
The process will be designed using SuperProDesigner and the approach is to develop a
program and to evaluate the performance in order to develop an efficient separation system.
The fractionation will be performed using a two-stage separation process based on a
prehydrolysis step with a weak acid dilution (H2SO4 + water) where the hemicellulose will be
dissolved in water, followed by an organosolv process with ethanol as solvent and , where
cellulose remains in the solid phase while lignin is dissolved. A possible approach to avoid
degradation reactions of hemicellulose sugars is prehydrolysis of the hemicellulose fraction,
this way the hemicellulose fraction does not have to be exposed to the relatively severe
process conditions required for delignification. The resulting solid residue from the aqueous
treatment consists mainly of lignin and cellulose and contains less inorganic and organic

10
extractives compared to the starting material. As a consequence, this lignin-cellulose residue
seems a better feed-stock for the production of pure lignin and cellulose by organosolv
delignification than the raw biomass [24].
In comparison with Kraft pulping which is the predominant chemical pulping technology,
organosolv pulping has significant economic and environmental advantages. The emission of
reduced sulfur as formed in Kraft pulping can be eliminated. Recovery of ethanol and
dissolved lignin can be carried out with a distillation system and a precipitation system,
resulting in a substantial saving in capital cost for a Kraft recovery system [2]. The extraction
of lignin and recovery of ethanol can be done in the same step, without requiring another
stage of separation for the ethanol recovery which doesn’t happen in the Kraft pulping process.

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 2. DESIGN OF THE PROCESS
A prehydrolysis step followed by an organosolv process has been modelled based on the
experimental data given by Ir. Edwin Keijsers and values found in the literature. The process
has been modelled using the simulation program SuperPro Designer as a continuous process.
The kinetics of the reaction were unknown for the continuous process, so they were set taking
into account the reaction equations and separation values according to the results obtained in
the experimental work done by the FBR group.

The process has been designed taken into account several sources from literature [1] [2],
where it was researched the use of a prehydrolysis step before the organosolv process.
However, there are some differences in the main separation steps and in the downstream
process of the extraction of the products.

As it can be seen in [2], the fractionation is based on a process with two separation steps: a
prehydrolysis at different temperatures from 160°C to 190°C and different concentrations of
sulfuric acid that works as a catalyst in the hydrolysis of the hemicellulose and an organosolv
process with temperatures from 190°C to 220°C and an ethanol/water ratio of 60/40% w/w,
after each one of the processes, there is a centrifugation step where the solids are removed
from the liquid stream. The lignin extraction it then treated again with another mixture of
ethanol/water at the same ratio, in order to remove the lignin already dissolved that was still
present after the centrifugation, and finally treated with a stream cold water 3:1 w/w in order
to reduce the solvent content and precipitate the lignin.

Figure 1. Functional block diagram of experiments done in [2] for fractionation of lignocellulose.

In the process explained in [1] that can be seen in Figure 2, the process is also based in the
same two separation stages as before in [2]. The main differences are that this process is more
based on the pH of the process to do the separation steps. The prehydrolysis is done this time
with steam instead of water + H2SO4, as in the process mentioned before. There is no
presence of sulfuric acid as catalyst in this first separation, however, it is used later after the
prehydrolysis, to reduce it to a pH of 2 by adding 20% sulfuric acid at room temperature,
which led to lignin precipitation that was still present after the hydrolysis of hemicellulose.

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The hemicellulose recovery will be then carried out by using ethanol, which has been reported
in literature [25] that can effectively precipitate the hemicellulose. The stream containing
most part of lignin and cellulose was treated with ethanol in order to hydrolyze the lignin and
make the cellulose remain in the solid phase, then a washing step to separate the cellulose
from the lignin/ethanol mixture. Cellulose was obtained as a solid product and lignin was
treated with acid again in order to precipitate the lignin.

Figure 2. Functional flow diagram of process shown in [1] for fractionation of lignocellulose.

The functional block diagram in Figure 3 shows the steps in the design of the process studied
in this report. For further information of the process and characteristics of the equipment used
like size, material of construction or purchase cost, see Appendix.

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 Figure 3. Block diagram of lignocellulosic biomass pretreatment (prehydrolysis followed by organosolv
process).

There were some assumptions that had to be done during the process:

- The experimental data used for the prehydrolysis and organosolv process during the
steps was given by Ir. Edwin Keijsers based on experiments done in FBR department
and also from some experimental data from [2] (See chapter 4, Table 11). It wasn’t
taken into account the degradation of the glucose (cellulose and hemicellulose) and
arabinose that forms hemicellulose.
- The efficiency of the centrifugation step wasn’t known, the calculations were based on
the hypothesis that after each centrifugation step, there should be at least 1/3 part of
outlet stream in solid phase.
- In this study the hemicellulose that is dissolved in the process is referred as xylose.
This is not completely accurate as the hemicellulose also contains arabinose and other
compounds. The data for the other components could not be found so it was assumed
that all the hemicellulose present in the process was in form of xylose

In the prehydrolysis the lignocellulose is suspended in the acidified water (20 mM), which is
sprayed onto the raw material and then held at temperatures between 175°C and pressure of
10 bar with a liquid-to-solid (L/S) ratio of 7.5 L/kg dry biomass [2]. A substantial part of the
xylose reacts further to furfural and degradation products like humins and lignin-furfural
condensates and when the temperature is above 175°C the formation of these by-products is
too high, so the temperature chosen is 175°C, when the maximum yield of monomeric and

14
oligomeric xylose (44% in total) is obtained [2]. The mixture is heated with high pressure
steam. The hydrolysis of hemicellulose occurs, releasing monomeric sugars and soluble
oligomers from the cell wall matrix into the hydrolysate. The use of a prehydrolysis step prior
to organosolv delignification was found to improve the yield of xylose (hemicellulose
dissolved) and the enzymatic cellulose digestibility [24]. The hemicellulose removal increases
porosity and improves enzymatic digestibility, with maximum enzymatic digestibility usually
coinciding with complete hemicellulose removal [7]. The stream is then taken to a flash
system to remove water, which can be also recycled to the feed stream of water and as it is in
vapor phase at 100 °C, it can also be used to heat the mixture of water and sulfuric acid before
the prehydrolysis step. Then, there is a centrifugation to separate the solid from the liquid
phase containing the hemicellulose dissolved, and another washing with water to make sure
that the hemicellulose dissolved that hasn’t been able to be separated in the previous
centrifugation is now removed.

To remove the sulfuric acid that was used in the prehydrolysis as a catalyst, Ca(OH)2 was
used for precipitation as Ca(SO4) and then through decanter separation from the stream
containing the xylose (hemicellulose dissolved). This way, we make sure the sulfuric acid is
not present during the extraction of hemicellulose, and also is a safety issue in case there is
some problem of accumulation of the acid during the process, it can be well corrected by the
use of this equipment.

All the reactions that take place in this step are of first order, the equations are as follows and
the values of the kinetics are expressed in Table 1:

+ → (1)

→ + (2)

+ → (3)

Table 1. Value of kinetics for reactions during the prehydrolysis step.

Rate reaction Value
(min-1)
k1 3.0 E-02
k2 3.6 E-03
k3 4.3 E-04

The values of the rate reaction kinetics shown in Table 1, have been calculated taken into
account the data from [2], where it is specified the amount of each component that is
hydrolyzed during the reaction (for more information about the reaction in prehydrolysis see
Appendix).

The pulp resulting from the prehydrolysis step is further processed with an ethanol–water
ratio of 55:45% w/w to obtain a slurry with L/S ratio of 10 L solvent/kg biomass [2].
Apparently the lignin becomes more stable due to the aqueous pretreatment and is therefore
harder to extract during the organosolv step, also the removal of the salts during prehydrolysis
may play a role in reduction of organosolv delignification since salts have been reported to

15
catalyze organosolv pulping. To compensate for this reduction in the delignification, the
process temperature of the organosolv fractionation step has been increased to over 175°C [2].

A higher organosolv reaction temperature improves both the delignification, the hydrolysis of
residual xylan and the enzymatic digestibility of the resulting pulp. When the temperature
reaches 220°C, the lignin efficiency is lower, possibly because the high temperature applied
causes formation of smaller lignin fragments, which are more difficult to precipitate from the
organosolv liquor upon water addition [24]. At a temperature of 200°C the delignification is
high and the formation of these small fragments is minimum [24]. After the organosolv
process, there is another flash system that is used to remove water and ethanol, that can be
recirculated to the organosolv process keeping the same weight fraction. Following the
centrifugation, there is another washing step similar to the one used in the prehydrolysis, but
this time using a mixture of ethanol/water 55:45% w/w to remove the lignin dissolved that
couldn’t be separated in the centrifugation step. The reason why the ratio of ethanol/water is
different from previous experiments [1] [2] is because of some issues with the simulation
program, where it was not possible to a good distillation for the recovery, so it was chosen a
lower ratio according to Figure 4, where it can be seen that the extraction also works. After
the centrifugation steps ethanol and water are recovered by distillation and as then lignin
precipitation is carried out. As the proportion of the organic solvent decreases, in this case
ethanol, the solubility of lignin in the mixture is reduced and then the precipitation takes place.
Figure 4, shows the amount of lignin dissolved depending on the ethanol/water ratio used in
the several experiments, which supports the theory that when the ethanol is removed from the
system the lignin present precipitates and is dissolved in the mixture [27]

Figure 4. Fraction of lignin dissolved depending on the organic solvent proportion.

The reactions that take place during the organosolv process are like in the previous step of
first order:

+ → (4)

+ → (5)

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 + → (6)

Table 2. Value of kinetics for reactions during organosolv process.

Rate reaction Value
(min-1)
k1 3.8 E-02
k2 5.2 E-04
k3 8.7 E-03

A summary of all the equipment needed during the process has been done, with all the
information required during the simulation. It can be seen in the chapter APPENDIX.

17
3. RESULTS

Figure 5. Flowsheet of the fractionation of lignocellulose through prehydrolysis and organosolv process.

18
The experimental values were based on experimental data from literature [24] and
experimental values given by Ir. Edwin Keijsers from FBR group and didn’t change when the
process was up scaled to 10,000 T/year. The sources for experimental data was based on batch
processes and they were assumed the same for continuous process developed in this study.

In chapter 2, the process was separated in two main parts: prehydrolysis and organosolv
process. The process model obtained from the simulation of the process using SuperPro
Designer is showed in this chapter in Figure 5.

After prehydrolysis, the centrifugation divides the stream into one based on the solid phase
containing mostly cellulose, lignin and hemicellulose that hasn’t been dissolved in the
previous reaction and the liquid phase containing water, furfural and hemicellulose dissolved
(xylose).

The results obtained for the extraction of hemicellulose in S-123 are expressed in Table 2 as
follows:
Table 3. Results obtained in the product stream of xylose.
Flowrate (kg/h) Mass composition (%)
Water 8,880.37 97.84
Xylose 154.75 1.70
Furfural 30.82 0.34
Dissolved lignin 10.97 0.12

The yield obtained in the process for the hydrolysis of hemicellulose reaches 54%.

After the organosolv process, most lignin is dissolved in the water and cellulose remains
almost intact in the solid phase. The results for the extraction of cellulose after drying in S-
142 are expressed in Table 3 as follows:

Table 4. Results obtained in the product stream of cellulose.

Flowrate (kg/h) Mass composition (%)
Cellulose 412.25 79.81
Lignin 56.57 10.95
Hemicellulose 26.80 5.19
Ethanol 9.90 1.92
Water 8.26 1.60
Dissolved lignin 1.88 0.36
Xylose 0.83 0.16
Dissolved cellulose 0.02 4.5E-03

The yield obtained in the process for the extraction of cellulose reaches 80.25%.

Once the ethanol has been recovered, the lignin that had been dissolved previously in the
organosolv process precipitates and it can be dried and extracted. The results for the
extraction of lignin after drying in S-145 are expressed in Table 4. The difference between
lignin and solid lignin is that the first one is the solid part from the beginning of the process
that hasn’t been dissolved in water in the organosolv process and the other one is the lignin
that has been dissolved and later precipitated when the ethanol was removed

19
 Table 5. Results obtained in the product stream of lignin.
Flowrate (kg/h) Mass composition (%)
Solid Lignin 203.74 79.81
Cellulose 30.55 10.89
Water 14.64 5.22
Lignin 9.60 3.42
Xylose 6.50 2.32
Dissolved cellulose 4.60 1.64
Hemicellulose 4.54 1.62
Dissolved lignin 3.12 1.11
Ethanol 2.95 1.05
Furfural 0.12 0.04

The yield obtained in the process for the extraction of lignin reaches 60%.

SuperPro Designer can also give reports about economic evaluation of the process, pointing
the most important factors to see if the process can be feasible or not. The reports are given
automatically by the program, no calculations were made.

Table 6 gives the amount of materials used in the process and the amount of utilities used in
the process.
Table 6. Amount of chemicals used every year during the extraction process.
Material Flowrate (kg/year)
Ca Hydroxide 75,398.40
Cellulose 4,068,504.00
Ethanol 5,090,351.76
Hemicellulose 2,260,368.00
Lignin 2,712,600.00
Sulphuric Acid 99,712.80
Water 87,259,891.39
Heat transfer agent Flowrate (kg/year)
Cooling water 9,128,317,740.28
Steam 103,464,111.15
Steam (High P) 31,169,003.97

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Table 7 shows the costs associated with the materials and the utilities:

Table 7. Annual cost of chemicals used during the extraction process.

Material Annual cost (€)
Ca Hydroxide 145,812
Cellulose 203,425
Ethanol 2,792,427
Hemicellulose 113,018
Lignin 13,563
Sulphuric Acid 5,105
Water 8,693
Total 3,404,064
Utilities Annual cost (€)
Std Power 120,847
Steam 908,130
Steam (High P) 455,957
Cooling water 333,840
Total 1,818,774

Table 8 shows the power demand that requires the process every year and the cost :

Table 8. Power demand in the process.

Std Power Kw-h/year
R-101 : P-4 (Hemicellulose hydrolysis) 156,511.96
BC-101 : P-2 (Belt conveying) 9,041.47
SC-101 : P-5 (Screw conveying) 28,835.11
R-103 : P-13 (Organosolv process) 180,058.47
DDR-101 : P-22 (Dryer cellulose) 21,336.64
DDR-102 : P-25 (Dryer lignin) 21,828.50
GR-101 : P-30 (Grinder) 904,147.20
Unlisted Equipment 82,609.96
General Load 247,829.88
Total 1,652,199.19
Std Power (0.10 €/Kw-h) €/year
Total 165,219.92

The total cost of the process can be seen in Table 9, where the investment, operating and
revenues cost are shown.

Table 9 shows the raw materials costs used in the process and the selling prices fixed for the
main products produced:

21
 Table 9. Cost of raw materials per kg used during the process.
Raw materials cost €/kg €/year
Ca Hydroxide 1.75 145,812
Cellulose 0.05 203,425
Ethyl alcohol 0.55 2,792,381
Hemicellulose 0.05 113,018
Lignin 0.05 135,630
Sulphuric acid 0.44 51,050
Water 1E-04 8,693
Total 2.89 3,450,009
Selling price products €/kg Revenues (€/year) (Table 10)
Cellulose 1.75
Hemicellulose 2
Lignin 1.5
Furfural 1.5

Table 10 shows a summary of the profitability analysis of extraction process:

Table 10. Executive summary and profitability analysis of extraction process.

Investment costs(€) 34,397,000
Operating costs (€/year) 5,223,000
Revenue xylose and furfural (€/year) 1,461,672
Revenue lignin (€/year) 3,106,753
Revenue cellulose (€/year) 7,421,039
Total revenue (€/year) 11,989,464
Steam savings (€/year) 252,576
Cooling water savings (€/year) 106,043
Total savings (€/year) 358,619

The operating costs don’t include the data of labor-dependent, facility-dependent and
laboratory/QC/QA. The operating costs shown in Table 10 were calculated as the sum of raw
materials and utilities used in the process.

22
 4. DISCUSSION
In this report there are some similarities with two processes mentioned in chapter 2 [1] [2] but
there are also some differences that can be appreciated:

- The prehydrolysis step is based on the information present in [2], where the
hemicellulose is dissolved in water with the presence of sulphuric acid as catalyst. The
temperature chosen has been selected according to the optimal one calculated in [2],
which was 175°C and p=10bar with 60% of hemicellulose hydrolysed, indeed he
formation of furfural as by-product is also taken into account in the design of the
process. There is a centrifugation step following the prehydrolysis and a washing step
with water, where the hemicellulose that has been previously dissolved in the process
and hasn’t been separated in the centrifugation is removed.
- In the organosolv process, the ratio chosen is very similar to the one used in [2] where
it was 60:40 % w/w, whereas in this study is 55:45% w/w due to better performance in
the simulation program. The temperature and pressure were also selected according to
literature [2] [26]. There is also a washing step after it with the same EtOH/water ratio.

The main differences between these last two processes shown before and our research are:

- After the prehydrolysis step, before centrifuging, a flash has been installed in order to
remove some water that came from the reactor. The water that removed was in vapour
state, and then could be recycled to the beginning of the process to save money in the
purchase of water in feed stream (S-105) and also it was used to heat the mixture with
sulphuric acid before the hydrolysis of hemicellulose to 100 °C.
- In this study, the presence of sulphuric acid that is used as catalyst is considered as a
toxic compound. As it can be read in [1] its presence can be removed by adding lime
(Ca(OH)2) and then recovered as gypsum (CaSO4). After the washing step and
centrifugation the hemicellulose dissolved is separated from the gypsum with a
decanter.
- In our process, the stream containing lignin with water and ethanol is treated in several
distillation towers where ethanol is removed along with water and then lignin
precipitates, in this way ethanol can be easily recovered and be reused in the
organosolv process and washing step. Unlike the processes developed for now using
only organosolv processes without prehydrolysis [7], now it is not required such a
high ethanol/water ratio to hydrolyse the lignin, which is translated into less spending
on distillation processes for the recovery of ethanol. The use of distillation columns
also saves the problematic using strong acids (H2SO4) to precipitate the lignin [1],
which can be very corrosive and must be recycled to lower the cost.
- Both streams containing cellulose and lignin at the end of the process, are submitted to
drum drying to remove the water present and obtain the products as purified as
possible.

During the design of the process with SuperPro Designer, there were some assumptions that
had to be done to develop the process. The values for the kinetics in both reactions of

23
hydrolysis of hemicellulose (prehydrolysis) and lignin (organosolv) were missing because for
the moment, the experiments have not been done in continuous mode in experimental work in
the lab.

According to some data found in literature [2] and some experiments done by FBR
department in the pilot plant, following a batch process, the amount of the components that is
dissolved in the processes is presented in Table 11 as follows:

Table 11. Data for hydrolysis of three main components of hemicellulose in prehydrolysis and organosolv
process.
PREHYDROLYSIS ORGANOSOLV PROCESS
Lignin Hemicellulose Cellulose Lignin Hemicellulose Cellulose
% Dissolved 5 60 - 80 50 5
Data for hydrolysis of hemicellulose in prehydrolysis from [2], the rest of data obtained from lab
experiments done by FBR department

The kinetics used in both separation steps were supposed taking into account the data given in
Table 15 for a batch process.

Throughout the process, high amounts of water are used to dissolve the components or do
washing steps. The use of centrifugations is then really important to separate the products
dissolved from the ones that remain in the solid phase. Efficiencies for centrifugation
processes couldn´t be found in literature, it was assumed that after each centrifugation, in the
solid phase there was 1/3 of the total value of the stream in form of lignocellulose (cellulose,
hemicellulose and lignin that are not hydrolyzed and remain in the solid phase in the same
form as the feed stream of the process).

The process requires high amount of energy. The program could also do an energy recovery
report where it was included which processes could be heated using other items on the process.

The energy recovery of the process done with the simulation process is expressed in Table 12
as follows:

Table 12. Energy recovery of the process for operations requiring cooling (Heat sources).
Operation Cooling load Tin Tout Cooling agent Recipient Matching %
(kcal/h) (°C) (°C)
P-21: 3,468,615.1 92.8 92.8 Cooling water P-25: DRY-1 26.7
DISTILL-1 [25°C-30°C]
P-23: 1,157,464.7 92 92 Cooling water P-22: DRY-1 78.2
DISTILL-1 [25°C-30°C]

In the distillation columns used for the recovery of ethanol and water and therefore the
precipitation of lignin, it is necessary to cool down the out streams. P-25: DRY-1, is the dryer
system used for the purification of the lignin, while P-22: DRY-1, is the one used for the
purification of the cellulose.

According to the report given by the simulation program, 26.7% of the heat requirements of
the first distillation column can be given by P-25: DRY-1 and 78.2% for the second
distillation column can be given by P-22: DRY-1.

24
During the process a high amount of ethanol and water is removed through the flash systems
and distillation after the organosolv process where ethanol is removed so lignin can
precipitate and then be extracted. In the first part of the process after the prehydrolysis, in the
goal to remove water from the process it was used a flash system (P-7 / V-101), where it was
removed 13% of the water in vapor phase. This stream composed entirely by water was
recovered to the beginning of the process and mixed with the feed stream of water (S-147),
just before mixing it with the sulfuric acid. Indeed, the high temperature of the vapor stream
made the temperature of the stream that enters in the prehydrolysis step increase and then less
utilities had to be used in this step. The data of this recovery can be seen in Table 13 as
follows:

Table 13. Data for recirculation from first flash system (P-7 / V-101) with water stream S-147 (Outlet
stream, S-105).
Add-Inn stream (kg/h) 1,111.65
Process stream (kg/h) 7,442.95
Outlet stream (kg/h) 8,554.60

After the organosolv process, there are several steps where a mixture of ethanol and water is
removed: in the flash system (P-16 / V-105), first distillation column (P-21 / C-101) and
second distillation column (P-23 / C-102). The feed stream (S-152) used in the organosolv
process had an EtOH/water ratio (55:45 w/w %), the same as the stream that was used for the
washing step in P-18 / V-106 to remove the remaining dissolved lignin. The streams coming
from these equipment mentioned before, were mixed in order to get the same ratio as S-152.
The data of the streams that were mixed to be recirculated can be seen in Table 14 as follows:

Table 14. Data for recirculation streams used in the process.

S-140 S-111 S-141 S-143 S-148
Ethanol (kg/h) 4,583.55 870.87 3,712.68 1,089.1 920.77
wi 0.56 0.56 0.56 0.49 0.60
Water (kg/h) 3,633.08 690.26 2,942.8 1,130.58 618.22
wi 0.44 0.44 0.44 0.51 0.40
Total (kg/h) 8,216.63 1561.13 6,655.48 2,219.68 1,538.99

S-111 and S-141 come from the same source (S-140) that is the stream from the first
distillation column (P-21 / C-101). The first one is recirculated to the washing step in P-18 /
V-106 while the second one is sent to the organosolv process with the other two streams S-
143 and S-148. The results for the recovery streams are shown in Table 15 as follows:

Table 15. Data for recirculation streams that are reused in the organosolv process.
Add-In stream Process stream Outlet stream
Ethanol (kg/h) 5,722.58 572.81 6,295.4
wi 0.55 0.55 0.55
Water (kg/h) 4,691.59 470.4 5,161.99
wi 0.45 0.45 0.45
Total 10,414.17 1,043.21 11,457.39

25
With the data presented in Table 14, 91.1% of the ethanol and 37.6% of water can be
recovered. It should be studied if the recovery of ethanol can be higher installing another
distillation column to recover the ethanol, as in other researches [28], it is said that it can
reach 95% recovery.

The economical evaluation of the process is shown in chapter 3 (Results). The most important
data that can be used to see if the process can be feasible or no is shown in Table 16 as
follows:

Table 16. Economical evaluation of the process.

Investment costs(€) 34,397,000
Operating costs (€/year) 5,223,000
Total revenue (€/year) 11,989,464
Total savings (€/year) 358,619
To calculate the operating costs, it wasn´t taken into account the labor cost.

Comparing the results obtained from Table 16, it can be seen that the revenues obtained from
selling cellulose, hemicellulose and lignin, along with the savings from heat integration, are
significantly higher that the money spent in raw materials and utilities (operating costs). The
labor costs were not considered because the program SuperPro gave too high default values,
the same happens with CAPEX values, the equipment costs were too high, and therefore were
not considered in this study.

26
 5. CONCLUSIONS
In this work a process is proposed for the production of hemicellulose, cellulose and lignin.
The process is based on conversion data from literature and data from FBR department. To
obtain these three products, this study proposes to use another separation step before the
organosolv process in order to avoid the degradation that hemicellulose can suffer due to the
extreme conditions it works with. The previous step was based on a prehydrolysis using a
mixture of water and sulfuric acid 20 mM to provoke the hydrolysis of the hemicellulose.
Then, the organosolv process is applied to hydrolyze the lignin present in the process, which
didn’t require so high temperatures as the process without prehydrolysis. The simulation
model for the fractionation of lignocellulose shows high yields for the three main components
recovery with the pretreatment proposed in this study.

The high yields obtained in the simulation process supports this theory and the easy recovery
of the ethanol makes the process very interesting to look into. Being the operating costs lower
than the total revenue obtained from the sale of the products, it is interesting to think that a
new path can be found to optimize the process to try to design a future pilot plant taking into
account this time some economic data that hasn’t been looked into here like the labor-
dependent, facility-dependent and laboratory/QC/QA costs. This study is a first step to design
a process to fractionate lignocellulose and obtain intact the three main components cellulose,
hemicellulose and lignin it is formed, continuous process seems to be possible and it is a
promising interesting path to investigate into, however it requires more study to optimize the
process in terms of heat integration, recovery of materials and search of kinetics that can work
in continuous processes.

27
 6. ACKNOWLEDGEMENTS
I would like to thank a lot of people who have supported me not only in this last year of
master thesis but also in my bachelor and in my master, and without them it couldn’t have
been possible.

First of all, I would like to thank prof. Dr. JH (Harry) Bitter and Dr. Van Boxtel (Ton) as head
of the department and supervisor for the opportunity to work at the Chair group Biobased
Chemistry & Technology (BCT) during this internship. Many thanks to Dr. M. Fdez. Polanco
and Dr. R.B. Mato for making this exchange possible and give me the chance to enjoy this
experience.

I am very grateful to my supervisor Dr. Van Boxtel (Ton) and Ir. Keijsers (Edwin) for all the
things they have taught me during this last 4 months, in both academic and personal field.

Out of work, I would like to express my love and gratitude to my family, specially my parents
Jesús and Nines, my brother Javier and my sister Elena. Thank for all your support and
encouragement, for believing in me and for being there in the good moments and especially in
the bad moments.

28
 7. REFERENCES
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extraction (2011). Zehua Liu, Pedram Fatehi, M. Sarwar Jahan, Yohghao Ni. Bioresource
Technology, Vol.102, 1264-1269.

[2] Fractionation of wheat straw by prehydrolysis, organosolv delignification and enzymatic

hydrolysis for production of sugars and lignin (2012). W.J.J. Huijgen, A.T. Smith, P.J. de
Wild, H. den Uil. Energy Research Centre of The Netherlands (ECN). Vol. 114, 389-398.

[3] High added value valorisation of lignin for optimal biorefinery of lignocellulose to energy
carriers and products (2011). Richard J.A. Gosselink. Energy Research Central of The
Netherlands.

[4] Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production (2007).
Michael E. Himmel, Shi-You Ding, David K. Johnson, William S. Adney, Mark R. Nimlos,
John W. Brady, Thomas D. Foust. Sustainability and Energy, Vol. 315, 804-807.

[5] Agro-industrial lignocellulosic biomass a key to unlock the future bio-energy: A brief
review (2014). Zahid Anwar, Muhammad Gulfraz, Muhammad Irshad. Journal of Radiation
Research and Applied Science, Vol. 7, 163-173.

[6] Lignocellulosic biorefineries: concepts and possibilities (2014). Kennet F. Reardon.

Advances in Plant Biology, Vol.4, 255-267.

[7] Literature review of physical and chemical pretreatment processes for lignocellulosic
biomass (2010) P.P.H Harmsen, W.J.J. Huijgen, L.M. Bermúdez López, R.C.C. Bakker.

[8] Lignin Production by Organosolv Fractionation of Lignocellulosic Biomass (2010),

Wouter Huijgen, Paul de Wild & Hans Reith, International Biomass valorisation congress in
Amsterdam, The Netherlands.

[9] Conversion of cellulose, hemicellulose and lignin into platform molecules:

biotechnological approach. Anders Frolander (2011), Borregaard Industries Ltd, Norway.

[10] Ethanol from lignocellulosic biomass: techno-economic performance in short-, middle-

and long-term (2005), Carlo N. Hamelinck, Geertje van Hooijdonk, André PC Faaij. Biomass
and Bioenergy, Vol.28, 384-410.

[11] A roadmap for conversion of lignocellulosic biomass to chemicals and fuels (2012) ,
Stephanie G Wettstein, David Martin Alonso, Elif I Gürbüz and James A Dumesic, Current
Opinion in Chemical Engineering, Vol. 1, 218-224.

[12] Pretreatment and fractionation of lignocellulosic biomass for production of biofuel and
value-added products (2012), Yoo, Chang Geun. Graduate Theses and Dissertations. PAPER
12700.

29
[13] Ethanol-based organosolv fractionation of wheat straw for the production of lignin and
enzymatically digestible cellulose (2013). Jelle Wildschut, Arjan T. Smith, Johannes H.Reith,
Wouter J.J. Huijgen. Vol. 135, 58-66.

[14] Biorefinery–systems (2004). Kamm B., Kamm M., Chem. Biochem. Eng. Q. Vol. 181 1–
6.

[15] Deconstruction of lignocellulosic biomass to fuels and chemicals, Shishir P. S.

Chindawat (2011). Annual Review of Chemical and Biomolecular Engineering, Vol. 2, 121-
145.

[16] Lignocellulosic feedstock biorefinery for co-production of chemicals, transportation,

fuels, electricity and heat (2009), J.H. Reith, R. van Ree, R. Capote Campos, R. R. Bakker,
P.J. de Wild, F. Monot, B. Estrine, A.V. Bridgwater, A. Agostini, Energy Research Centre of
the Netherlands

[17] P. Industrial biotechnology for production of bio-based chemicals (2007). Hatti-Kal,

R.Iornvall, U. Trends Biotechnol. Vol. 25, 119-124.

[18] Ethanol production from wheat straw by Saccharomyces cerevisiae and Scheffersomyces
stipitis co-culture in batch and continuous system (2014). Pinar Karagöz. Melek Özkan.
Bioresource Tehcnology, Vol. 158, 286-293.

[19] High-performance hydrolysis of cellulose using mixed cellulase species and

ultrasonication pretreatment (2004). Imai, M., Ikari, K. and Suzuki, I. Biochemical
Engineering Journal, Vol. 17, 79-83.

[20] Features of promising technologies for pretreatment of lignocellulosic biomass (2005).

Nathan Mosier, Charles Wyman, Bruce Dale, Richard Elander, Y.Y.Lee, Mark Holtzapple,
Michael Ladisch. Bioresource Technology, Vol. 96, 673-686.

[21] Fundamental factors affecting biomass enzymatic reactivity (2000). Vincent S. Chang,
Mark T. Holtzapple. Journal of Applied Biochemistry and Biotechnology. Vol. 84-86, 5-37.

[22] Hydrolysis of lignocellulosic materials for ethanol production: a review, Ye Sun, Jiayang
Cheng (2002). Bioresource Technology, Vol. 83, 1-11.

[23] Fractionation of lignocellulosic biomass with the ionic liquid 1-butylimidazolium

hydrogen sulphate (2014), Pedro Verdía, Agnieszka Brandt, Jason P. Hallett, Michael J. Ray
and Tom Welton. Royal Society of Chemistry, Vol. 16, 1617.

[24] Lignin precipitation on the pulp fibers in the ethanol-based organosolv pulping (2007).
Yongjian Xu, Kecheng Li, Meiyun Zhang. Colloids and Surfaces A: Physicochem. Eng.
Aspects, Vol. 301, 255-263.

[25] Extraction and characterization of hemicelluloses and cellulose from oil palm trunk and
empty fruit bunch fibres (1999). Sun, R.C., Fang, J.M., Mott, L., Bolton, J. J. Wood Chem.
Technol. Vol 19 (1-2), 167-185.

30
[26] Organosolv process (2012). Alex Berlin, Mikhail Y. Balakshin, Raymond Ma, Gutman
Vera Maximenko, Darwin Ortiz. Publication number CA2803177 A1.

[27] Features of promising technologies for pretreatment of lignocellulosic biomass (2005).

Nathan Mosier, Charles Wyman, Bruce Dale, Richard Elander, Y.Y. Lee, Mark Holtzapple,
Michael Ladisch. Bioresource Technology, Vol. 96, 673-686.

[28] Ethanol recovery process (2010). Anurag P. Mairal, Alvin Ng, Richard W. Baker, Ivy
Huang, Jennifer Ly. Publication number US7732173 B2.

[29] Direct ethanol production form hemicellulosic materials of rice straw by use of an
engineered yeast strain codisplaying three types of hemicellulolytic enzymes on the surface of
xylose utilizing Saccharomyces cerevisiae cells (2012). Sakamoto, T., Hasunuma, T, Hori, Y.,
Yamada, R., Kondo, A. Journal of Biotechnology, Vol 158, 203-210.

31
8. APPENDIX
Code Type of equipment Function Remark
Transport solid Convey solids, with a
P-2 / BC-101 Belt conveying lignocellulose to the specific loading rate
grinder of 200000 L/m2h
Size reduction of
P-30 / GR-101 Grinder lignocellulose to a more -
suitable particle size
Adjust flow of Add-In
stream and mix it with
Outlet stream mass
P-3 / MX-105 Custom Mixing the Process stream to
flow of 8554.6 kg/h
reach an outlet stream
mass flow
Mix streams of water
P-1 / MX-101 Mixer -
and sulfuric acid
Mix streams of
acidified water from
P-6 / MX-102 Mixer mixer P-1 / MX-101 -
with lignocellulosic
biomass from grinder
Convey the slurry
stream made by Convey solids, with a
P-5 / SC-101 Screw conveying biomass and acidified specific throughput of
water to the 200000 L/m2h
prehydrolysis process
Out stream of the
reaction:
hemicellulose (60%
Hydrolysis of xylose. 20% remains
hemicellulose and solid, 20% furfural)
furfural as by-product. lignin (5% lignin is
Continuous Kinetic
P-4 / R-101 Execute reactions (1), dissolved). The
Reaction
(2), (3) at 175°C and reaction used a L/S
P=10 bar with volume ratio of 7.5 L / kg dry
ratio of 90% biomass. Data from
[2] and experimental
data of FBR
department.
Flash works with a
user-defined
Remove water of the vapor/liquid split and
P-7 / V-101 Phase change : Flash stream from the reactor under adiabatic
P-4 / R-101. conditions of
1.013bar and
100.34°C
Filtrate water with Filter at a flux of 250
Rotary vacuum hemicellulose and L/m2h, to cake
P-8 / RVF-101
filtration lignin dissolved from porosity 0.30 v/v,
cellulose, hemicellulose wash solvent flowrate

32
 and lignin that is still is 60.32 L/h
solid
Mix liquid streams
from the centrifugations
P-8 / RVF-101 and P-
P-11 / MX-103 Mixer -
10 / RVF-103 (after
reaction and washing
step with water)
Removal of sulfuric
acid, making it react
Continuous with Ca(OH)2 and then Reaction works under
P-12 / R-102 Stoichiometric precipitate in form of adiabatic conditions
Reaction CaSO4 and at 1bar
H2SO4 + Ca(OH)2 →
CaSO4 + H2O
Decant two
Separate hemicellulose
immiscible liquid
P-14 / V-104 Decanting dissolved in water from
phases, the pressure is
the precipitates CaSO4
1.013bar
Washing step
Do another washing
continuously and it
step with water to
works under adiabatic
remove the xylose that
conditions and
P-9 / V-102 Washing water hasn’t been filtrated
pressure is 1bar. The
before in the
washing used a L/S
centrifugation P-8 /
ratio of 3L / kg dry
RVF-101
biomass
Filtrate solid stream
Filter at a flux of 250
that comes from P-8 /
L/m2h, to cake
Rotary vacuum RVF-101 and separate
P-10 / RVF-103 porosity 0.40 v/v,
filtration remained hemicellulose
wash solvent flowrate
dissolved in water from
is 60.32 L/h
the rest
Adjust flow of Add-In
stream and mix it with
Outlet stream mass
P-15 / MX-107 Custom mixing the Process stream to
flow of 11457.38 kg/h
reach an outlet stream
mass flow
Out stream of the
reaction:
hemicellulose (50%
Hydrolysis of lignin
xylose) lignin (80% is
and hemicellulose that
dissolved),
remained solid. Execute
Continuous Kinetic cellulose(5%
P-13 / R-103 reactions (4), (5), (6) at
Reaction dissolved). The
195°C and P=30 bar
reaction used a L/S
with volume ratio of
ratio of 10L solvent
90%
(ethanol) / kg
biomass. Data from
[2] and experimental

33
 data of FBR
department
Flash works with a
Remove water and user-defined
ethanol of the stream vapor/liquid split and
P-16 / V-105 Phase change: Flash
from the reactor P-13 / under adiabatic
R-103 conditions of
1.013bar and 101.4°C
Filtrate water with Filter at a flux of 250
mostly lignin dissolved L/m2h, to cake
Rotary vacuum
P-17 / RVF-102 and low amounts of porosity 0.30 v/v,
filtration
hemicellulose and wash solvent flowrate
cellulose dissolved is 60.32 L/h
Adjust flow of Add-In
stream and mix it with
Outlet stream mass
P-26 / MX-106 Custom mixing the Process stream to
flow of 1688.51 kg/h
reach an outlet stream
mass flow
Do another washing
step with EtOH / water Washing step
55:45 to remove the continuously and it
Washing EtOH /
P-18 / V-106 lignin dissolved that works under adiabatic
water 55:45
hasn’t been filtrated conditions and
before in the pressure is 1bar
centrifugation
Filtrate water with Filter at a flux of 250
mostly lignin dissolved L/m2h, to cake
Rotary vacuum
P-19 / RVF-104 and low amounts of porosity 0.40 v/v,
filtration
hemicellulose and wash solvent flowrate
cellulose dissolved is 60.32 L/h
Mix liquid streams
from the centrifugations
P-20 / MX-104 Mixer P-17 / RVF-102 and P- -
19 / RVF-104 (after
reaction and washing
Distill continuously at
an R/Rmin ratio of
1.25. Ethyl alcohol
Distillation Do the recovery of the
P-21 / C-101 and water were
continuous column ethanol/water 55:45
selected as light and
heavy key
components
Distill continuously at
Do the recovery of the
an R/Rmin ratio of
ethanol/water 55:45 that
1.25. Ethyl alcohol
Distillation is still in the stream
P-23 / C-102 and water were
continuous column from the previous
selected as light and
distillation column P-21
heavy key
/ C-101
components
P-22 / DDR-101 Drum drying Dry the stream that Final solids

34
 contains mostly temperature: 30°C
cellulose and low and dry at a rate of 40
amounts of lignin and kg/m2h
hemicellulose.
Cellulose is considered
as product
Out stream of the
Due to the removal of reaction:
ethanol lignin is hemicellulose (50%
Continuous Kinetic
P-24 / R-104 precipitated as the xylose) lignin (80% is
Reaction
solubility of lignin dissolved),
decreases cellulose(5%
dissolved)
Cool down gas stream
from P-16 / V-105 to
Cool with cooling
P-29 / HX-101 Heat Exchanger recirculate to the
water to 50 °C
organosolv process in
P-13 / R-103
Divide stream to Split flow of streams.
recover EtOH/water in Split 19% to top
P-27 / FSP-101 Splitter
the washing step and in stream.
the organosolv process
Dry the stream that
contains mostly lignin
Final solids
and low amounts of
temperature: 30°C
P-25 / DDR-102 Drum drying cellulose and
and dry at a rate of 40
hemicellulose. Solid
kg/m2h
lignin is considered as
product
Mix streams from both
distillation columns and
P-28 / MX-108 Mixer -
flash process containing
EtOH/water 55:45

35
36