Sugarcane Bagasse Pretreatment Processes

In recent years, the application of Fenton reaction to lignocellulose

pretreatment has been attempted, which is naturally present in fungi to
degrade wood (Arantes et al., 2012). Moreover, Fenton reaction is widely
used in waste water pretreatment (Li and Zhang, 2014). The Fenton reaction,
a non-selective reaction, can oxidize organic compounds without preference
(Kiril Mert et al., 2010). Its initiators are ferrous ions and hydrogen peroxide.
In the reduction–oxidation reaction, radicals like hydroxyl radicals are
generated, which could strongly oxidize the organic compounds. Besides, it
has been found that Fenton reaction can increase their susceptibility to
cellulase enzyme (Jain and Vigneshwaran, 2012), and improve the
degradation of lignin (Arantes et al., 2011).

a.) Sequential extractions of dewaxed SCB (Alkali and Alkaline

Peroxide)
Sequential treatment of dewaxed SCB with distilled water at 55 (C for 2
h with or without first ultrasonic irradiation for 40 min, 0.5 M NaOH, 0.5%,
1.0%, 1.5%, 2.0%, and 3.0% H2O2 under alkaline condition, resulted in
dissolution or degradation of 95.5 of the original hemicelluloses, and 91.7 of
the original lignin, yielding 44.7% cellulose, which contained 6.0 associated
hemicelluloses and 3.4 % bound lignin.
b.) Isolation of cellulose by Delignification with Acidified Sodium
Chlorite
The extractive free bagasse (40 g) was first treated with distilled water
for 2 h at 700C. Further the water-soluble free sample will be delignified with
1.3% sodium chlorite at pH 3.5-4.0, adjusted with 10% acetic acid, at 75 (C
for 2 h. Finally, the holocellulose was extracted with 10% potassium
hydroxide for 10h at 200C. After filtration, the residues were washed
thoroughly with distilled water and 95% ethanol and dried in an oven for 16 h
at 60 (C. Yielding 44.7% cellulose.
c.) Isolation of cellulose by Acetic Acid – Nitric Acid mixture
The method for isolation of celluloses with an 80% acetic acid 70%
nitric acid mixture (10:1, v/v). SCB sample (5.0 g) was weighed into 200 ml
Pyrex tubes. Subsequently, 100 ml 80% aqueous acetic acid (w/w) and 10 ml
70% nitric acid (w/w) was added. The tubes were sealed using screw-caps
fitted with Teflon liners and placed into an oil bath set at the required
temperature at 1200C for 20 min. When the tube was removed from the oil
bath and cooled, 60 ml of distilled water was added, and the reagent was
decanted off. The residue was then thoroughly washed with distilled water
and 95% ethanol to remove the nitric acid and extraction breakdown
products. The residue was then dried in an oven at 60 (C for 16 h. Yielding
43.0% Cellulose content.
d.) Sugar Cane Bagasse Alkaline Pre-Treatment Process
The first step of the pretreatment was carried out using 20% (w/v) of
bagasse immersed in a 2% (v/v) or 3.66% (w/w) sulfuric acid solution. The
mixture was subjected to a temperature of 121 °C for 30 min. The resulting
solid fraction was washed until pH 7.0 and then it was dried at 40 °C in a
circulating drying oven.
The second step of this pretreatment was carried out using 20% (w/v) of
bagasse
immersed in a 4% (w/w) sodium hydroxide solution. The mixture was also
subjected to a temperature of 121 °C for 30 min. The pH of the mixture was
adjusted to 7.0 using HCl after the reaction. The solid fraction was washed
three times with tap water to remove dissolved sugars and solubilized lignin,
and stored at 4 °C until used. Before the use of the bagasse in assays, the
humidity was measured to convert amounts to a dried weight basis
(Guilherme et al., 2015).

e.) Combined Hydrothermal and Alkaline Pretreatment

The hydrothermal pretreatment was carried out using a high-pressure
reactor (Stainless Steel PARR Reactor 4520-1 L, Series 4520 Bench Top
Reactors 1 L Parr Instruments Company, USA), 10% of solids, 100 rpm, 20
bar of initial pressure with nitrogen, 170 °C of process temperature reaching
35 bar; the rise time of the temperature was 40 minutes, the process time
was 40 minutes and the cooling time was 15 minutes. Because this process
did not use acid catalysts, preventing corrosion of process equipment, and
producing less inhibitory compounds of enzymatic hydrolysis, the solid
fraction was not washed. The resulting solid fraction was dried at 40 °C in a
circulating drying oven (Tecnal model TE–394/1, Piracicaba/Brazil). The
second step of the pretreatment was carried out under the same conditions
as presented in the second step of the combined acid and alkaline
pretreatment (Guilherme et al., 2015).

f.) Alkaline Pretreatment

This pretreatment was carried out under the same conditions
employed in the second step of the combined acid and alkaline pretreatment
(Guilherme et al., 2015).
g.) Peroxide Pretreatment
 The pretreatment with hydrogen peroxide was carried out using 4%
(w/v) of biomass immersed in a 7.35% (v/v) or 8.15% (w/w) hydrogen
peroxide solution. The pH of the hydrogen peroxide solution was adjusted to
11.5 with sodium hydroxide. The mixture was stirred at 100 rpm for 1 h at
room temperature using a mechanical stirrer (Tecnal model TE–139,
Piracicaba/Brazil). Due to the exothermic nature of the process, a
temperature increase was observed and the final temperature was 80 °C.
After the reaction, the liquid fraction was discarded and the solids washed
with water. The solid fraction was washed fifteen times with tap water and
stored at 4 °C until used. Before the use of the bagasse in assays, the
humidity was measured to convert amounts to a dried weight basis
(Guilherme et al., 2015).
Fermentation of Glucose to Ethanol by Yeast (Saccharomyces
Cerevisiae)
Fresh Fleischmann’s bakers’ yeast (Saccharomyces cerevisiae) was
washed three times and suspended in a 0.1 M NaH 2PO4 solution. The
fermentations were carried out in a liter Erlenmeyer flask with 500 ml. of the
yeast suspension. The flask was in a water bath and the suspension was very
rapidly stirred by a large glass-covered, motor-driven, magnetic stirrer for
the duration of the experiments. Before adding glucose, the atmosphere was
displaced by nitrogen and the system was allowed to come to equilibrium.
After the glucose was added, the carbon dioxide production was m.easured
in the gas burette, care being taken that the system was at atmospheric
pressure at all times. The temperature of the water bath, the temperature of
the gas burette, and the atmospheric pressure were also recorded. It was
assumed that equilibrium was maintained between the gaseous and
dissolved carbon dioxide. Thus the t.otal carbon dioxide production was
taken as the sum of the observed burette reading and the calculated carbon
dioxide in solution. The anaerobic fermentation of 500 mg. of anhydrous
glucose by a fresh suspension of bakers’ yeast. The suspension contained
2.5 gm. (wet weight) of yeast made up to 500 ml. with 0.1 M NaH2PO4.
The glucose consumption curve shows that the sugar had completely
disappeared after 180 minutes. At that time 0.72 of a glucose equivalent had
been converted into carbon dioxide and ethanol, and the hydrolyzable
polysaccharide content of the cells had increased from 0.51 to 0.71 of a
glucose equivalents, while 1.00 equivalent of glucose had been utilized.
Therefore, 72 per cent of the sugar was fermented to carbon dioxide and
ethanol, 20 per cent was assimilated, and 8 per cent formed other products
(probably glycerol, succinic acid, etc.).
Simultaneous saccharification fermentation (SSF)
 Simultaneous saccharification fermentation (SSF) is generally
acknowledged as a process to trim cellulase inhibition by glucose and
simplify the operation due to the integration of saccharification and
fermentation, thus greatly enhancing fermentation efficiency (Hasunuma and
Kondo, 2012).
The SSF was conducted in 25 ml penicillin bottles with a working
volume of 15 ml and a solid loading of 4% (w/w). The yeast was inoculated to
the medium along with enzymes added at a yeast inoculum dosage of 10%
(v/v). Cellulase was added at a loading of 35 FPU/g of SCB to all samples. b-
glucosidase was added at a loading of 20 U/g if necessary. Bottles were
incubated in a rotary shaker at 30 0C, 150 rpm for 192 h during which 0.1 ml
of samples were withdrawn periodically. The fermentation products were
analyzed by Waters 2414 HPLC (Milford, LA, the US) equipped with refractive
index detector and Aminex HPX-87H column ((Bio-Rad, Hercules, CA). Upon
calculations, where 1.11 is the coefficient of glucose obtained from glucan;
1.14 is the coefficient of xylose obtained from xylan; 0.51 is the coefficient of
ethanol obtained from glucose; and 0.46 is the coefficient of ethanol
obtained from xylose.

Enzymatic Hydrolysis via Fungus Trichoderma viride

Enzyme complexes derived from the fungus Trichoderma viride have
been found effective in the conversion of cellulosic wastes into glucose
syrups. Trichoderma viride, a fungus found in nature, is the only fungus
known that produces a specific enzyme which is capable of reacting with the
crystalline fraction of the cellulose molecule.
Cellulose can be converted to glucose by either acid hydrolysis or
enzymatic processes [1,2]. The use of enzymes is more advantageous. When
using acid, expensive corrosion-proof equipment is required. Moreover, the
crystalline structure of cellulose makes it resistant to acid, therefore the
temperature and acid concentrations needed to achieve hydrolysis also
cause decomposition of the resulting sugars. Consequently, the process
must be balanced so that the rate of hydrolysis is high enough to
compensate for decomposition of the desired products. Glucose yields of
approximately 50 percent of the weight of cellulose used have been
obtained.
PET MANUFACTURING PROCESS
 Figure __ Traditional Manufacturing Process of PET
The conventional PET process consists of two discrete plant sections.
The first part consists of melt phase reaction used to produce copolymers
with an intrinsic viscosity (IV) suitable for textile applications. But when very
high molecular weights are desired, as is the case for bottle grade PET
resins, the polymerization may be carried out in stages. The traditional
Buhler process integrates four typical stages for producing bottle grade PET:
crystallization, annealing, solid state polymerization (SSP) and cooling.
(Guichon Valves)
CHOICE OF PROCESS
Sugar Cane Bagasse Alkaline Pre-Treatment Process
The amounts of solid fraction obtained after the pretreatment
processes were 0.26, 0.33, 0.55 and 0.21 g/g raw material respectively for
the combined acid and alkaline, combined hydrothermal and alkaline,
alkaline, and peroxide pretreatment. The higher amount of solid fraction in
the alkaline pretreatment was caused by the low conversion of
hemicellulose, which remained in the solid fraction. A considerable amount
of foam was formed during the hydrogen peroxide pretreatment and this
foam influenced the high loss of biomass observed in this pretreatment. The
small amounts of solid fraction that were observed were caused by the
solubilization of part of the bagasse in the liquid fraction.
Composition of the Raw Material and the Solid Fraction of
Pretreated Bagasse
Treatment Cellulose Hemicellulos Lignin Ash
e
Combined Acid 62.69 10.76 7.81 3.84
and Alkaline
Combined 58.02 10.79 5.99 7.79
Hydrothermal
and Alkaline
Alkaline 45.95 28.05 3.22 0.54
Peroxide 51.09 18.75 0.85 2.95
Sequential 44.7 6.0 3.4
extractions
dewaxed SCB
Delignification 44.7 5.7 1.6
with Sodium
hypochlorite
(KOH)
Acetic Acid- 43.6 3.2-4.3 0.2-0.6
Nitric Acid
Treatment
 The combined acid and alkaline pretreatment and the combined
hydrothermal and alkaline pretreatment were able to increase by 68.5 and
61.0%, respectively, the amount of cellulose in the bagasse composition.
The combined acid and alkaline pretreatment and the combined
hydrothermal and alkaline pretreatment were able to reduce the amount of
hemicellulose in the bagasse by 60.7 and 58.7%, respectively. All
pretreatments were able to reduce the amount of lignin by at least 50%, with
the alkaline pretreatment presenting the highest lignin reduction. The table
below shows the %lignin removal of different concentrations of NaOH. With
87.3% lignin removal, NaOH concentration of 1.5%, operating at 30 min
appeared to be the highest.

Enzymatic Hydrolysis via Fungus Trichoderma viride

Enzyme complexes derived from the fungus Trichoderma viride have
been found effective in the conversion of cellulosic wastes into glucose
syrups. Trichoderma viride, a fungus found in nature, is the only fungus
known that produces a specific enzyme which is capable of reacting with the
crystalline fraction of the cellulose molecule.
Cellulose can be converted to glucose by either acid hydrolysis or
enzymatic processes [1,2]. The use of enzymes is more advantageous. When
using acid, expensive corrosion-proof equipment is required. Moreover, the
crystalline structure of cellulose makes it resistant to acid, therefore the
temperature and acid concentrations needed to achieve hydrolysis also
cause decomposition of the resulting sugars. Consequently, the process
must be balanced so that the rate of hydrolysis is high enough to
compensate for decomposition of the desired products. Glucose yields of
approximately 50 percent of the weight of cellulose used have been
obtained.
The first step is the production of the enzyme. This is accomplished by
growing the fungus Trichoderma viride in a culture medium containing
shredded cellulose and various nutrient salts. Following its growth, the
fungus culture is filtered and the solids discarded. The clear straw-colored
filtrate is the enzyme solution that is used in the saccharification reactor.
Prior to its introduction into the reactor, the enzyme broth is assayed for
cellulase activity and its acidity is adjusted to a pH of 4.8. Milled cellulose is
then introduced into the enzyme solution and allowed to react with the
cellulase to produce glucose sugar. Note that saccharification takes place at
atmospheric pressure and at a temperature of 50°C. The unreacted cellulose
and enzyme is recycled back into the reactor, and the crude glucose syrup is
filtered for use in chemical or microbial fermentation processes to produce
chemical feedstocks, single-cell proteins, fuels, solvents, etc. The key to this
process is production of a high quality cellulase enzyme complex from
‘Trichoderma viride capable of hydrolyzing insoluble crystalline cellulose.

Fermentation of Glucose to Ethanol by Yeast (Saccharomyces

Cerevisiae)
Fresh Fleischmann’s bakers’ yeast (Saccharomyces cerevisiae) was
washed three times and suspended in a 0.1 M NaH 2PO4 solution. The
fermentations were carried out in a liter Erlenmeyer flask with 500 ml. of the
yeast suspension. The flask was in a water bath and the suspension was very
rapidly stirred by a large glass-covered, motor-driven, magnetic stirrer for
the duration of the experiments. Before adding glucose, the atmosphere was
displaced by nitrogen and the system was allowed to come to equilibrium.
After the glucose was added, the carbon dioxide production was measured in
the gas burette, care being taken that the system was at atmospheric
pressure at all times. The temperature of the water bath, the temperature of
the gas burette, and the atmospheric pressure were also recorded. It was
assumed that equilibrium was maintained between the gaseous and
dissolved carbon dioxide. Thus the t.otal carbon dioxide production was
taken as the sum of the observed burette reading and the calculated carbon
dioxide in solution. The anaerobic fermentation of 500 mg. of anhydrous
glucose by a fresh suspension of bakers’ yeast. The suspension contained
2.5 gm. (wet weight) of yeast made up to 500 ml. with 0.1 M NaH2PO4.
 The glucose consumption curve shows that the sugar had completely
disappeared after 180 minutes. At that time 0.72 of a glucose equivalent had
been converted into carbon dioxide and ethanol, and the hydrolyzable
polysaccharide content of the cells had increased from 0.51 to 0.71 of a
glucose equivalents, while 1.00 equivalent of glucose had been utilized.
Therefore, 72 per cent of the sugar was fermented to carbon dioxide and
ethanol, 20 per cent was assimilated, and 8 per cent formed other products
(probably glycerol, succinic acid, etc.).

Ethanol Purification Process through Azeotrope Distillation of

Ethanol
The purification process of ethanol is normally done through a method called
fractional distillation, which can lead up to a concentration of 95.6 percent by
weight. M

The fractional distillation of ethanol refers to the process of separating a

mixture into its different components or fractions by heating them up to a
certain temperature that will cause some of the fractions to evaporate.

After distillation, the resulting mixture will be composed of 95.6 percent

ethanol and 4.4 percent water. At 95.6% ethanol and 4.4% water, the
ethanol mixture is considered as an azeotrope with a 78.2 degrees Celsius
boiling point.

Catalytic Dehydration of Ethanol to Ethylene through Fluidized Bed

Reactor
Alumina-based catalysts are used in most of the current industrial
reactors of ethylene production. Ethanol at the concentration of 95% (w/w) is
used as raw material and the operation conditions are a temperature of
300−500 °C, a pressure of 0.1−0.2 MPa, and space velocity of 0.1−1 h −1 .
The ethylene yield can reach 94−99%. Pearson et al. have made systematic
researches on the influencing factors of the process operation of ethanol
dehydration to ethylene, including reaction temperature, operating pressure,
space velocity, the water content in raw material of ethanol, and so on.
 Zhou T. et al. studied the ethanol (mass concentration is 99.7%)
dehydration to ethylene reaction on the composite catalyst of SAPO-11/
HZSM-5 and found that the increase of the catalyst acidity helped to improve
the ethanol conversion rate and ethylene yield, when the pressure was 0.1
MPa, the temperature was 513 K, the space velocity was 1.2 h−1, the
ethanol conversion rate was 99.19%, and ethylene selectivity was 98.77%;
when the ethanol conversion rate and ethylene selectivity both reached
99.00%, the reaction temperature of the catalyst was 60 K lower than those
of HZSM-5 and SAPO-11.

Ethylene Oxidation via Silver Catalyst

Silver/alumina catalyst is the type of catalyst used, which drives the
selectivity of the reactions towards ethylene oxidation. The silver allows for
oxygen adsorption on its surface, which forms an ionized superoxide. The
ethylene is reactive with this superoxide, resulting in the formation of
ethylene oxide. This catalyst is capable of producing the 80.9% conversion.
At Tin/Tout=270/4900F, Pin= 230 psig.

Reactor Inlet Reactor Outlet

C2H4, lbmol/hr 12865 9481
O2, lbmol/hr 3164 0
EO, lbmol/hr 0 2795
CO2, lbmol/hr 1141 2319
H2O, lbmol/hr 0 1178
CH4, lbmol/hr 10833 10833
CH4, lbmol/hr 28003 26606

Referring to table, the conversion of ethylene to ethylene oxide is

80.9%. The selectivity of the ethylene oxide reaction to the combustion
reaction was 4.75. In other words, the ratio of ethylene used to form
ethylene oxide to the amount of ethylene used to form CO2 and water was
4.75 to 1.

Hydrolysis of Ethylene Oxide

Ethylene oxide reacts with water to form ethylene glycol, and then
further reacts with ethylene glycol and higher homologues in a series of
consecutive reactions as shown in the following equations:
 In the process either a 0.5 to 1.0% sulphuric acid (H 2SO4) catalyst is
used at 50 to70oC for 30 minutes or, in the absence of the acid, a
temperature of 195oC and 185 psi for 1hour will form the diol. The formation
of higher glycols is inevitable because ethylene oxide reacts faster with
ethylene glycols faster than with water. The most important variable is the
water-to-oxide ration, and the production of diethylene glycol (DEG) and
triethylene glycol (TEG) can be reduced by using a large excess of water. A
90 percent yield is realized when the ethylene oxide/water molar ratio is 1:5-
8. The advantage of the acid-catalyzed reaction is no high pressure;
however, the thermal reaction needs no corrosion resistance and no acid
separation step. The crude glycols are dehydrated and then recovered
individually as highly pure overhead streams from a series of vacuum-
operated purification columns. Ethylene glycol (boiling point: 197.6 oC) is
readily vacuum distilled and separated from the diethylene glycol (boiling
point: 246oC, density: 1.118, flash point: 124 oC) and triethylene glycol
(boiling point: 288oC, density: 1.1274, flash point: 177 oC). Since ethylene
glycol is produced in relatively high purity, differences in quality are not
expected.