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J. of Supercritical Fluids 46 (2008) 299321
Review
From plant materials to ethanol by means of
supercritical uid technology
Christian Schacht, Carsten Zetzl, Gerd Brunner
C).
The process, nevertheless, comprises some steps, which have
to be improved for the efcient use of ligno-cellulosic material,
e.g. pre-treatment, hydrolysis, fermentation, and the concen-
tration step to absolute alcohol. This will be discussed in the
following. More questions are still open for the use of lignin,
which mostly is used for energy supply, for the waste water, and
for the solid residues.
4. State of the art: conventional processes of the 1st and
2nd generation
The conversion of biomass to ethanol generally includes three
steps: The hydrolysis of the cellulose and hemi-cellulose into
monomer sugars, the fermentation of the sugars to ethanol as
well as the purication of ethanol. Although different ways of
hydrolysis have been studied, enzymatic treatment provides the
greatest potential to lead the technology towards a successful
competition with conventional fuel technologies [1214].
Unlike 2nd generation processes, 1st generation processes
basically use starch, contained in grains or seeds (e.g. corn,
wheat, rye, etc.) as a starting material for ethanol production.
2nd generation processes try to make use of the whole plant,
e.g. corn stover, rye stover, bagasse or grass. Processes, which
directly use sugar solutions, e.g. from sugar cane or sugar beet,
start with their process line after the saccharication. 1st gen-
eration processes can be subdivided into dry milling and wet
milling processes [15].
Wet-milling plants, which comprise about 25% of the capac-
ity in the USA, produce ethanol together with a variety of
co-products. In contrast, dry grind plants are designed for the
production of ethanol and produce animal feed as co-product.
Capital cost are lower than for wet milling plants.
Ligno-cellulosic biomass can be pre-treated and enzymati-
cally hydrolyzed to yield a mixture of sugars including glucose,
galactose, arabinose, and xylose [16].
So far, no commercial plant is operating on the basis of cellu-
losic material. There is a demonstration plant, operated by Iogen
Corporate, Ottawa, Canada. The process is basically the same
as for starch-based plants with appropriate steps for the pre-
treatment of the biomass. Technological innovations claimed by
Iogen include [17]: Pre-treatment by a modied steamexplosion
process, new, highly potent and efcient cellulase enzyme sys-
tems, separate hydrolysis and fermentation using a multistage
hydrolysis process, advanced micro-organisms and fermenta-
tion systems that convert both C6 and C5 sugars into ethanol,
energy efcient heat integration, water recycling and co-product
production.
4.1. Pre-treatment
An effective pre-treatment includes the decrease of the cel-
lulose crystallinity by the removal of hemi-cellulose and lignin
as well as the increase of the cellulose porosity [18,19]. Fur-
thermore, the formation of decomposition products, that inhibit
further process steps, have to be avoided, size reduction of the
feed stocks has to be obviated and energy demands as well as
costs have to be minimized.
Duringthe last 25years plentyof pre-treatment-methods have
been developed, which can be reviewed at other places [1214].
Whereas dilute acid pre-treatments are already commercially
available, treatment of biomass with liquid hot water (LHW)
is still being worked at on laboratory scale [11,20]. However,
due to its simplicity, low generation of inhibiting by-products
and projected yields of up to 98% LHW pre-treatment exhibits
a great potential, and Hamelinck [11] points out the need to
perform further research on this pre-treatment method.
Lignin hinders water-molecules to enter the cellulosic micro-
brils andthus inhibits the actionof enzymes. Inaddition, crystal
structure of cellulose reduces the surface available for contact
with the enzymes [13].
Pre-treatment of ligno-cellulosic biomass should conse-
quently eliminate steric hindrance and enlarge porosity of the
substrate. Hereby, reaction of mono-sugars to degradation prod-
ucts must be avoided since it reduces yields and produces
inhibiting compounds.
Dilute acid pre-treatment was a long-time preferred pro-
cedure and has been reviewed repeatedly [12,18,2123]. The
substrate is contacted with dilute sulphuric acid (0.51.5 wt.%),
or other acids like nitric acid or hypo-chloric acid, at tempera-
tures of 160220
T 100
14.75
, (3)
with t as reaction time (min) and T as temperature (
C).
4.2.2. Enzymatic saccharication
Due to the disadvantages of acid catalyzed hydrolysis,
enzymatic hydrolysis is nowadays preferred. The reaction mech-
anism of the enzymatic hydrolysis is discussed in the literature
([5,10]), but not fully understood, yet. To enable the reac-
tion, the enzyme (cellulase) must be coupled to the substrate,
which requires the substrate to exhibit a certain size and type
of the three-dimensional structure. Different types of cellulases
are known. Exogluconases act at the end of the chains, while
C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321 303
endogluconases split the chains. Both actions lead to water
soluble oligomers which are transformed by -glucosidase or
cellobiase to glucose [40,41].
The costs for the enzymes are a substantial part of pro-
duction costs for bio-ethanol. For recycling the enzymes, the
enzymes must be separated from the product ow, for repeated
use, enzymes must remain in the reactor and the product ow
must be removed. A detailed discussion is beyond the scope of
this contribution.
4.3. Fermentation of C5 and C6 sugars to ethanol
Saccharomyces cerevisiae (bakers yeast) produces adenosin-
triphosphate (ATP) during anaerobic fermentation via glycoly-
sis. Pyruvate is formed and is transformed to ethanol. In total,
2 mol ethanol and 2 mol CO
2
are formed per mol of glucose. To
make use of most of the ligno-cellulosic material, pentose sug-
ars must also be transformed to ethanol. Genetically modied S.
cerevisiae is developed in order to transformglucose and xylose
at the same time [4244]. So far, glucose is transferred at much
higher rates than xylose.
4.4. Separation
The common process uses for separation of the ethanol a rst
distillation column, called beer column. Remaining solids and
the major part of water is separated in this column. Ethanol is
removed, together with CO
2
which was produced during the
fermentation, over top. CO
2
is washed out with water and this
stream is recycled to the bottom. The bottom ow contains
all the solids which are separated with a centrifuge. The liq-
uid ow in the centrifuge is concentrated with heat from the
distillation. Condensed water is returned into the process. The
product ow from this column contains about 37% ethanol.
Ethanol is enriched in another distillation column up to the
azeotropic concentration of 95%. To produce absolute alcohol,
various distillation methods have been developed and employed,
partially with compounds like benzene or tri-chlor-ethylene. A
more recent and more environmentally friendly process is the
removal of water by molecular sieve adsorption [25].
5. Supercritical/near critical uid technology
contributions
Recently, research has been carried out to compare hot liquid
water (LHW) pre-treatment to the treatment of biomass with
steam. The concept is a treatment of ligno-cellulose by sub-
critical pressurized water, eventually assisted by CO
2
-enhanced
hydrolysis.
Utilization of a steam treatment could signicantly lower the
water usage. However, due to the advantage of signicantly
lower hydrolysate inhibition, the main attention is being paid
on the development of LHW processes, which promises also
a higher conversion. Higher xylan recovery suggesting lower
generation of degradation products could be recognized for the
LHW treatment [45,46].
Fig. 1. Treatment of ligno-cellulosic material with liquid hot water.
Generally, an aqueous suspension of ligno-cellulose
(1020%) is treated at elevated pressures, to keep the water
in the liquid phase (Fig. 1). For an industrial application the
following scenario was developed for a LHW pre-treatment, in
which the products are already separated into different streams.
The biomass is contacted with water at temperatures from
170230
Cor higher.
Some oxygen is added (e.g. by in-line high-pressure electrolysis)
and the efuent streams are processed further.
Generally no particle size reduction is required for this kind
of pre-treatment [13,19,47]. The pioneer work regarding pre-
treatments with hot liquid water has been performed by Bobleter
and co-workers, who found out that hemi-cellulose could be
completely separated from the ligno-cellulose and enzymatic
digestibility of cellulose can be signicantly increased by treat-
ing the ligno-cellulosic material with hot compressed water in
ow through systems [48,49].
The contact time is one of the main variables determining
the efciency of the pre-treatment in which the hemi-cellulose
is removed from the biomass and the structure of the cellu-
lose is changed enabling accelerated enzymatic hydrolysis. The
feasibility of breaking chemical bonds with water are facili-
tated by the fact that water develops acidic characteristics at
high temperatures. The ion product K
w
of water increases with
the temperature up to a maximum of 6.34 10
12
at 250
C
resulting in a pH of 5.5 for water at a temperature of 220
C
[27].
By percolating biomass at temperatures of 200230
C and
residence times between0 minand15 min, Antal andco-workers
were able to achieve a total decomposition of hemi-cellulose and
90% yield of pentose sugars [50,51].
In Table 1 an overviewshows work carried out with hot liquid
water for pre-treatment of biomass [21,29,45,46,4959]. The
304 C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321
Table 1
Bibliography on liquid hot water pretreatment
Author Year Parameters Flow (mL/min) Operation Substrate Yield (% of the theoretical maximum)
Temperature (
C to 300
C [6365] and a
detailed kinetic investigation of the hydrolytic reactions of glu-
cose near the critical point was published by Kabyemela [66].
Also studies on hydrolysis of cellulose were available, but to our
knowledge the hydrolysis of starch had not been investigated
until end of the 90s.
Sakaki et al. [67] described the saccharication of cellulose,
starting from temperatures at 180
C, increasing to values to
above 280
C.
C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321 305
5.2.1. Type of reactor
For pre-treatment with hot liquid water three types of reactors
can be used: Batch, semi-continuous, and continuous reactors. In
batch-reactors the solid substrate (ligno-cellulosic biomass) as
well as the reaction medium (water) is reacted together without
adding or removing products during reaction time. In semi-batch
reactors a xed bed of biomass is contacted by a owof the reac-
tion medium, which is constantly added and removed, and may
be additionally recycled. Data from semi-continuous reactors
may be transferred to industrial scale reactors.
Continuous processes can be operated in a co-current and
a counter-current mode. Ligno-cellulosic biomass is mostly
contacted co-currently. A slurry of biomass and water is con-
tinuously pumped rst through a heat-exchanger and then kept
at constant reaction conditions in a ow-through reactor, ideally
at plug-ow conditions. Short residence times are easily real-
ized, but longer residence times can only be achieved with long
tubular reactors or a high recycle ratio. The problems for this
operation mode are connected with the continuous handling of
solid material, especially if higher pressures are involved. But
ground biomass (about 1 mm) can be pumped into the reactors
under any condition. High solids concentrations are also not easy
to achieve. Most experimental data are obtained therefore at low
concentrations and are not relevant for industrial application. A
solids concentration of at least 10 wt.% must be achieved for
practical and economic purposes.
5.2.2. Inuence of solids concentration in the feed
Since most experiments have been carried out at low con-
centration, the concentration dependence of the ligno-cellulose
decomposition is not clear. Most results indicate that an
increased biomass concentration results in a lower pH-value.
Results on xylan yield are differing. In a batch reactor no inu-
ence on yield of xylans could be found by Jacobsen and Wyman
[56], while Laser et al. [46] found an increased concentra-
tion of xylanes (beside higher concentration of furfural, and
an increased ethanol-yield after fermentation). Allen et al. [45]
determined a decreased decomposition with increasing biomass
concentration. All investigations agree on the decrease of pH
with increasing concentration of ligno-cellulose, which may
be explained by the increasing amount of organic acids being
formed.
5.2.3. Inuence of linear velocity
An increased ow rate in the reactor enhances degrada-
tion of the ligno-cellulosic substrate. This result was conrmed
by several groups [50,54,57] and may be considered as result
of the higher mass transfer rates at higher Reynolds-numbers.
Increasing (e.g.) the linear velocity from 2.8 to 10.7 cm/min,
the resulting xylans conversion increased from 60% to 82%
[58].
To avoid enhanced water consumption and decreased con-
centration of biomass, Liu and Wyman [59] used a xed-bed
reactor with periodically changing uid ow velocity. After a
period of zero ow rate, the xed bed was contacted with a hot
water ow, which was shut down after the pre-designed reac-
tion time and followed by another batch-reaction phase. The
result is in context with a normal extraction curve from solid
material. For the reduction of the specic solvent consumption
and increase of product concentration, it is to be preferred to
use several xed beds which are operated in a counter-current
mode.
5.2.4. Inuence of pressure
The inuence of the pressure on hydrolysis of biomass is basi-
cally limited to keeping the water liquid according to the process
temperature. Liu [60] could show that the pressure inuence on
the monomer concentration after pre-treatment can be neglected.
5.2.5. Inhibiting degradation products
During the decomposition process of biomass, degradation
products are formed, which inhibit the normal action of the
micro-organisms. Such degradation products are acetic acid,
which stems from the decomposition of hemi-cellulose [68],
hydroxy-methyl-furfural (HMF) and furfural. For these sub-
stances a strong inhibiting inuence on yeast could be shown.
Micro-organisms, active in ethanol fermentation from pentoses,
are more inhibited than those which ferment hexoses [69]. The
mechanism is explained by Palmquist [70,71]. Decomposition
of lignin produces phenolic compounds, which strongly inhibit
the action of yeast [69] and the enzymatic hydrolysis of ligno-
cellulose.
5.2.6. Carbonic acid addition
Dilute acid pre-treatment processes are applied on large scale
for biomass to ethanol processes [11]. Hemi-cellulose yields as
well as glucose yields after enzymatic treatment reach up to 90%
of the possible maximum (in [57]). The main disadvantages of
this process can be found in the application of the acid itself.
It results in a higher corrosion and the neutralization leads to
the formation of waste particles which have to be separated and
disposed. These drawbacks could be overcome by introducing
carbon dioxide to the HLWprocess instead of acid, because CO
2
can be neutralized by a pressure reduction. Van Walsum [62]
presented an increase of xylan hydrolysis by adding pressurized
CO
2
to the HLWtreatment. These results could not be replicated
with aspen wood being the feedstock in 2002 [72].
However, utilising corn stover an increase of xylose and furan
concentration was demonstrated by van Walsum and Shi [29].
Also, an increase of the nal pH was noticed in the LHW
treatment to which CO
2
was introduced. These results are in
agreement with the measurements from 2002, implicating the
assumption that the presence of carbonic acid represses the
formation of side products.
5.3. Contributions of TUHH laboratory
In this part a continuous process for the treatment of biomass
has been established, exhibiting the advantage of a process
without interruptions and frequent start-ups. The experimental
results are presented in this paper. Furthermore the effect of
simultaneous CO
2
supply has been investigated regarding xylan
yields as well as cellulose digestibility.
306 C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321
5.3.1. Hydrolysis of starch
The hydrolysis of starch with water and carbon dioxide at
elevated pressure and temperature was carried out with the aim
of optimizing the reaction conditions to obtain a maximumyield
of sugars, such as maltose, glucose and fructose. The hydrolysis
of starch is an acid catalyzed hydrolytic decomposition where
a COC linkage is cracked between two glycopyranose units
and a water molecule is inserted.
Experiments on starch were carried out in a tubular reactor of
4.02 m length an inner diameter of 6 mm and an outer diameter
of 10 mm. The used Inconel 600
C to
300
C and the pressure varied between 60 bar and 240 bar. Car-
bon dioxide inuence is expressed in degree of saturation, which
is the ratio of the added carbon dioxide to the maximum soluble
quantity of carbon dioxide in water at given conditions. Water
was saturated with nitrogen to exclude the inuence of oxygen.
Initial starch concentration was 0.2 wt.%, if not stated otherwise.
Fig. 2 shows the results of the hydrolysis of starch at 230
C and
240 bar.
The inuence of the concentration of carbon dioxide on the
formation of glucose is shown in Fig. 3.
Glucose yield is signicantly higher than without the use of
carbon dioxide. With log(R
0
) =4.5 the yield can be increased
from 5% to 60% by the addition of CO
2
. Increasing the initial
starch concentration up to 10 wt.% did not affect the glucose
yield signicantly (Fig. 4). Therefore, the results obtained with
a low initial concentration, seem to be transferable to higher
initial starch concentrations.
5.3.2. Liquefaction kinetics and conversion of cellulose and
starch
The overall degree of conversion of the biopolymer as well as
the yield and selectivity of the main reaction products are deter-
mined experimentally in a ow through type reactor. Additional
means like the acidication by carbon dioxide [60] to lower
Fig. 2. Product yields for conversion of starch under inuence of carbon dioxide
as a function of residence time at T=230
C.
Fig. 3. Glucose yields with different CO
2
concentrations as a function of resi-
dence time.
the pH and promote acid catalysed hydrolysis steps are being
investigated.
Micro-crystalline cellulose as purchased from Merck
(Avicel
C. A
further increase in temperature results in an even more rapid
degradation, yielding a complete conversion within seconds.
This behavior is illustrated in Fig. 6, which depicts the degree
of liquefaction on a carbon balance versus process severity at
constant pressure.
Fig. 6. Cellulose: degree of liquefaction f at different temperatures and residence
times at P=250 bar.
The calculated curves were derived assuming a rst order
kinetic for the cellulose decomposition for each applied
temperature. For this approach, the degree of conversion can
be described by Eq. (4):
ln(1 f) = k, (4)
where k denotes the reaction rate constant of the biomass
hydrolysis.
A common approach to express the temperature dependence
of the reaction rate constant is the Arrhenius lawwith k
S,j,0
being
the pre-exponential factor and E
A,j
the activation energy of the
reaction.
k
j
(T) = k
j,0
exp
E
A,j
RT
. (5)
The reaction rate constant for the degradation of cellulose
and of corn starch (obtained in an analogous manner) are stated
in Fig. 7.
For cellulose conversion, one may obtain
k
C,0
= 7.7 10
13
s
1
E
A
= 163.9 10
3
J/mol.
For corn starch conversion, one may obtain
k
S,0
= 5, 3 10
12
s
1
E
A
= 147.9 10
3
J/mol.
Regarding the temperature dependence, the reaction rate con-
stant at 250
C, 260
Cand 280
C, 260
C, and 280
C.
A marked rate enhancement of cellulose hydrolysis by carbon
dioxide addition could be determined at temperatures of 240
C
and 250
C and 280
C. There
is still a slightly increased rate of hydrolysis at 260
C, while
at 280
2H
+
+CO
3
2
.
(6)
Besides the kinetics of substrate hydrolysis, the investiga-
tion of product formation was of special interest. A detailed
knowledge of product formation is important to optimize reac-
tion conditions with respect to the selective production of desired
compounds, e.g. glucose or amino acids. Their product yields
are strongly affected by the choice of the reaction temperature as
well as by the residence time. For all temperatures a maximum
in yield is observable, which shifts to lower residence times as
the temperature increases.
The reaction rate constants of formation and decomposi-
tion can be determined by tting Eq. (7) to the experimentally
determined yields. With c
i,0
denoting the initial substrate con-
centration, the concentration of glucose can be calculated as
Fig. 9. Glucose yields after subcritical water hydrolysis of cellulose at different
residence times and temperatures at P=25 MPa; effect of dissolved CO
2
.
follows (Fig. 9):
c
i
=
k
f
i
k
d
i
k
f
i
c
i,0
[exp(k
f
i
t) exp(k
d
i
t)]. (7)
The rate constants for the formation and decomposition of
glucose (both from starch and cellulose) were obtained in an
analogous manner and are also stated in Fig. 10.
The constants for glucose conrm that its formation from
starch passes on faster than from cellulose due to the above
mentioned reasons. Furthermore, glucose is obviously insta-
ble under the conditions applied and accordingly consumed
by consecutive reactions. Different secondary degradation and
isomerization products were detected in this work, including
pyruvaldehyde, levoglucosan and HMF (from glucose) as well
as several carboxylic acids (from amino acids). However, a
Fig. 10. Rate constants of formation and decomposition for glucose (fromstarch
and cellulose).
C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321 309
closer inspection of these degradation products goes beyond
the scope of this work. The same applies for the different
by-products (mainly maltose, and oligomers and oligopep-
tides) formed by parallel reactions of the substrate according
to Fig. 10.
The optimumglucose yields, however, are obtained with resi-
dence times in the range of a few seconds up to several minutes,
depending on the reaction temperature. The maximal glucose
yield is reached at increased temperatures in combination with
short residence times. This nding is in accordance with lit-
erature results on cellulose hydrolyses at temperatures up to
400
C to 500
C with residence
times ranging from a few seconds to 3 min. Pure lignin
and ligno-cellulosic biomass could be liqueed by hydrol-
ysis up to 7080%. Efuents were subsequently treated by
biological degradation. Overall efciency of DOC (Dissolved
Organic Carbon) removal increased to 9095%. No toxic
effects on the micro-organisms were observed. The oxidation
of ligno-cellulose in near-critical water by hydrogen peroxide
converted all carbonaceous material to mainly gaseous prod-
ucts. Only about 10% of the initial carbon load remained
in the aqueous phase, with the main product being acetic
acid.
In contrast to the hydrolysis of pure cellulose, the hydrother-
mal degradation of the biomass residues from the methane
reactor yielded an incomplete liquefaction, which can probably
be attributed to the lignin present in the samples.
As a result, the model waste specied by ESA can be readily
converted by hydro-thermolysis without the addition of a cata-
lyst or an oxidant. Degrees of liquefaction up to 9095% could
be obtained on a carbon basis. Carbon in form of gaseous com-
pounds had a minor contribution and amounted to less than three
percent. Regarding the nitrogen balance, even higher degrees
(Table 2) of liquefaction up to 100% could be achieved. Both
the carbon and the nitrogen balance could be closed satisfacto-
rily. Based on these ndings, the conclusion is drawn that the
hydrothermal conversion of complex biomass is a suitable pro-
cess for the production of soluble hydrolysates, which can be
utilized by subsequent biological treatment.
In this context, the degree of liquefaction was calculated as
the ratio of dissolved carbon in the efuent to the total carbon
of the inuent suspension. The results reveal a strong increase
of the rate of liquefaction with increasing temperature in the
range of 250310
C. Afurther increase in
temperature results in an even more rapid degradation, yielding
a complete conversion within seconds (Fig. 11).
As in the case of cellulose, the addition of carbon dioxide
leads to distinctly increased rate of reaction. For the continu-
ous water oxidation of ligno-cellulosic biomass, the set-up was
partially modied. Due to the corrosive atmosphere of high-
temperature water in the presence of an oxidant, a new reaction
coil made of corrosion-resistant nickel alloy (Inconel
, Alloy
600, o.d. 6,35 mm, i.d. 2,13 mm) with an internal volume of
20 mL was installed downstream of the mixing point. The reac-
tor was placed in a 4 kW oven (Heraeus RO 7/75), which in
principle allows temperatures up to 1000
C. Under operating
conditions, reactor outlet temperatures up to 500
C could be
310 C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321
Fig. 11. Experimental results on model waste specied by ESA, computation
of carbon balance, P=25 MPa, initial solid concentration: 1 wt.%.
accomplished. Hydrogen peroxide was used as an oxidant. It was
directly introduced into the feed vessel and delivered to the reac-
tor along with the biomass in order to facilitate the experimental
procedure.
Water-soluble alkali lignin was used in these studies, since the
continuous processing of insoluble organosolv lignin was ham-
pered by the formation of lignin coagulates in the feed vessel and
lignin deposition in the reactor. As for the Cellulose, hydrogen
peroxide was used as the oxidant. It was directly introduced to
the feed vessel and delivered to the reactor together with lignin.
Time in the reaction zone was between 5 to 17 s for all experi-
ments. The conversion progress and the deduced rate constant,
considering a 1st order gasication of alkali lignin on a carbon
basis is shown in Fig. 12.
It can be concluded that the stoichiometric and over-
stoichiometric oxidant supply leads to an almost complete
oxidation of lignin in less than 20 s. About 10% of the inuent
Fig. 12. Conversion of alkali lignin to gaseous species on a carbon basis, inu-
ence of amount of oxidant and temperature, initial lignin concentration: 1 wt.%.
carbon remains in the liquid efuents as DOC at temperatures
up to 390
C.
Experiments on the hydrolysis of lignin were conducted
with organosolv lignin, which is essentially water insoluble at
ambient conditions. The results show that organosolv lignin
completely dissolves in near-critical water and undergoes sig-
nicant chemical modication.
The results discussed in literature and own experiments point
to the conclusion that a complete liquefaction of isolated lignin
by non-catalyzed hydrolysis in pure high-temperature water is
not feasible. At lower temperatures inthe well-subcritical region,
where the cleavage of the most widespread linkage, the -O-4-
bond, by hydrolysis should yield a high degree of degradation,
the portion of insoluble residues is still in the range of 3040%.
The formation of insoluble residues cannot be prevented even
under optimized conditions. Furthermore, the treatment in pure
water does not lead to the selective production of valuable com-
pounds but to a broad product spectrum. Treatment of lignin
in high temperature water led to the build-up of carbon-rich
residues, which eventually resulted in reactor clogging and pre-
vented the attempted continuous processing. Summing up these
aspects, the non-catalyzed hydrolysis of lignin in pure water
does not appear to be a promising approach.
This nding was derived from mass spectroscopy analyses
of soluble reaction products, which are illustrated exemplarily
by the total ion chromatogram in Fig. 13.
The chromatogram shows the existence of numerous degra-
dation products in considerable concentrations. Although some
major classes of degradation products could be identied, e.g.
phenols, phenol derivatives and other aromatic substances, a
complete identication and quantication of all reaction prod-
ucts is virtually impossible.
Comparing the results of ESA biomass with those from the
studies on lignin (and wheat straw), it can be seen that the
hydrolysis of the model waste yields much higher degrees of
liquefaction than in case of lignin and wheat straw, which can
be attributed to the much lower content of ligno-cellulose in
the model waste. Some ingredients, e.g. algae, do not have
any ligno-cellulosic structures at all. This repeatedly shows that
ligno-cellulose is the most persistent fraction of biomass and
points towards the potential of algae as a feedstock for bio-
ethanol production.
Fig. 13. Total ion chromatogram of products from Lignin degradation after
hydrolysis, T=417
C,
12 min for the glucose (due to the original content of starch
in the rice bran). The inuence of CO
2
is in the range of 10%,
which is non-signicant for these type of experiments.
6.4. Monomers and oligomers: kinetic modelling
The reactions are modeled in adaptation of the proposition in
chapter 4.2.1 as a sequential reaction, assuming two reactions
of rst order according Eqs. (1) and (2).
For the denition of the parameters k
1
and k
2
, a non-linear
regression has been executed. The sum of deviations of the
calculated concentration results from ve experimental val-
ues for each temperature program has been minimized via the
Newton-Approach. The model accordingEq. (1) was insufcient
when focusing on Glucose conversions, therefore the extension
according Eq. (2) has been chosen.
As the substrate type was identical, the adapting factor a must
be kept constant. Due to this, the average value of calculated
results for the fast-reacting fraction has been dened and xed.
Then, the regression has been repeated for obtaining the opti-
mized values k
1
and k
2
. Secondly, the error R
2
of the linear
regression for the logarithmic approach of the reaction constant
on the inverse temperature scale has been minimized.
The result of the modeling is presented in the following tables
and gures (Figs. 1521).
The reactionrate of the degradationis about one order of mag-
nitude higher than the rate for the formation of monomers. From
Fig. 15. Xylose concentration during hydrolysis; inuence of carbon dioxide
(a) P=75 bar without CO
2
and (b) P: saturation pressure (see original table).
that can be concluded that mono-sugars are rapidly reacting to
degradation products. In order to produce oligomers, which can
be treated by enzymes, the reaction rate constants should be kept
low. The lowest values are obtained at 200
C. The addition of
CO
2
signicantly enhances the ratio of k
1
/k
2
. Secondly, Fig. 22
Fig. 16. Glucose concentration during hydrolysis; inuence of carbon dioxide;
P=75 bar without CO
2
, P: saturation pressure (see original table).
Fig. 17. Arabinose concentrationduringhydrolysis; inuence of carbondioxide;
P=75 bar without CO
2,
P: saturation pressure (see original table).
C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321 313
Fig. 18. Concentration of xylose in dependency of the coefcient R
0
.
shows that the addition of CO
2
increases k
2
only marginally,
while k
1
is enhanced.
The concentration dependence of the oligomers shows the
hydrolysis of hemi-cellulose to soluble oligomers and the
sequential reaction to xylose monomers. The rst reaction step is
much faster than the formation of monomers. The reaction from
oligomers to monomers is the rate determining step. A reac-
tion temperature of 230
C.
The addition of carbon dioxide for the treatment of hemicel-
lulose (Fig. 23) will lead to a decrease of both process reaction
velocities. This nding contradicts to the observation of Fig. 22
(xylose oligomer conversion). One maydeduce a direct inuence
of the carbon dioxide saturation on the reaction rate. Conse-
quently, the reaction rate constants are not directly comparable
for the application with and without carbon dioxide saturation.
Analogous observations can be found for the hydrolysis of
cellulose. In the same way, a non-desired slow-conversion of
oligomers to monomers and direct fast-degradation to side
products shall be avoided by the application of moderate tem-
peratures.
6.5. Formation of degradation products
The hydrolysis of hemi-cellulose and cellulose to mono-
sugars may yield degradation products, which are at least
reducing the yield of fermentable sugars. HMF and furfural
could not be detected in the product ow (limit of detection:
40 mg/L).
Temperature has a dominant inuence on the formation of
organic acids. The addition of CO
2
inhibits the formation of
organic acids, as has also been reported by Walsum [29].
For an ethanol process, the total concentration of sugars is of
major important, since an enzymatic saccharication will fol-
low the thermal hydrolysis. The total concentration of sugars
is shown in the following diagrams, including the role of CO
2
(Figs. 24 and 25).
The picture of degradation products changes if residence
time is increased substantially. Rice bran was treated in a batch
reactor from 20 min to 60 min. The degree of liquefaction is
increasing even at low temperatures (160180
C and pH 5; at a pH-value of
4 or 6, activity is reduced to 10%of the maximumvalue) to a non
treated rice bran suspension resulted in a glucose concentration
of 730 mg/L. In pre-treated suspensions of rice bran the enzyme
treatment resulted in glucose concentrations up to 2100 mg/L
(Fig. 30).
Glucose concentration after combined pre-treatment and
enzyme-catalyzed hydrolysis decreases with increasing temper-
ature during pre-treatment, as has been reported by other groups
[27]. This may be due to reduced enzyme activity caused by
enhanced lignin concentrations in solution. The amount of dis-
solved lignin increases with temperature and residence time,
whichleads toreducedyieldof the enzymatic hydrolysis [53,57].
The maximum concentration of 2100 mg/L is obtained at log
(R
0
) of 3.5 to 4, which corresponds to a temperature for the
pre-treatment of 200
C at
Fig. 28. (a) Hot water rice bran liquefaction in a piston reactor at a pressure of
200 bar and (b) production of side products in function of time.
1 to 2 min residence time. This is about the same values as for
xylose and arabinose. If the feed suspension is saturated with
CO
2
, glucose concentrations remain constant in the range of
1000 mg/L and 1500 mg/L. The reason could be found in is the
reduced temperature dependence, when CO
2
is used, at higher
values for the temperature.
Fig. 29. Inuence of hot water hydrolysis on the liquefaction of rice bran and
yield of xylose and glucose.
316 C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321
Fig. 30. Glucose: concentration after enzymatic hydrolysis.
7. Fermentation to ethanol and separation with CO
2
Fermentation of the resulting mono-sugars to ethanol is a
technique which is known for a long time and usually carried out
with strains of bakers yeast (Saccharomyces cerevisiae). In order
to obtain ethanol from the sugar solution of about 100200 g/L,
containing C5- and C6-sugars, still a satisfying consortium of
micro-organisms has to be developed. This is outside of the
topic covered here, therefore, we assume that an aqueous ethanol
solution of 7 to 10% is available after fermentation, which now
has to be concentrated to 99.8 wt.% ethanol. Sakaki et al. [76]
contributed to the description of the fermentability of cellulose
decomposition products resulting froma near-critical hydrolysis
treatment.
SFE-technology can provide an alternative for the separation
of CO
2
solution, reducing the number of columns and applying
only separating agents inherent to the process [77,78].
In the past decade, numerous studies have been performed
to describe the separation efciency of the system carbon diox-
ide/ethanol/water at elevated pressures and temperature [79].
Vaporliquid equilibrium (VLE) data of CO
2
+ethanol +water
and its binary mixtures have been published in a wide range
of temperature and pressure. From an economic point of
view, gas extraction of ethanol +water mixtures should yield
ethanol of high purity to compete with conventional pro-
cesses. However, in order to get a high solubility of ethanol
in the vapor phase, many studies were carried out at condi-
tions of complete miscibility of ethanol and CO
2
[8082]. At
these conditions, the phase behavior of the ternary mixture
CO
2
+ethanol +water is of type I and anhydrous ethanol cannot
be produced.
One of the rst studies reporting the possibility to pro-
duce anhydrous ethanol by means of CO
2
without adding any
entrainer was by Nagahama et al. [83]. Experiments were car-
ried out at conditions of type II phase behavior. Further VLE
measurements of the mixture CO
2
+ethanol +water were per-
formed at Kobe Steel Ltd. in Japan (e.g. Furuta et al., [84,85])
at 10.1 MPa and 313 K, 323 K and 333 K. The separation factor
at 100 bar, 60
C (type I) .
C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321 317
of ethanol in water to approximately 1.25 at innite dilution of
water in ethanol.
Data have been concluded and transformed to Fig. 31.
The Ponchon-Savarit diagrams Fig. 31 can be interpreted
as follows: at a pressure of 100 bar and a temperature of
60
C, and
a stripping section (7%0% EtOH) at 160 bar and 60
C.
7.1. Estimation of the necessary number of theoretical
equilibrium plates
Numerical modeling tools or graphical methods allow to cal-
culate the number of equilibriumplates for a required product or
rafnate purity, provided a reux ratio and the number minimum
equilibrium plates has been dened.
The number of theoretical stages were calculated by the
Ponchon-Savarit method [88]. Fig. 32 illustrates calculated
results that are based on a feed mixture of 10 wt.% ethanol that
Fig. 32. Calculation of the number of theoretical plates for separation of
EtOHH
2
O: CC-SFE: 100 bar, 60
C. Although simula-
tion suggested the necessity of only 2 mixing plates, due to
constructive reasons, the apparatus was operating with 5 cells.
A pure water rafnate output (99.6% water) was achieved at
S/F=74, mixer-settler extract contains consequently 2030%
ethanol.
7.3. Design
With the information given above, it may directly be con-
cluded that a conventional counter-current SFE, operating at
100 bar and 60
C
Min diameter stripping section D=1.6 m, h =1 m,
vol =2 m
3
Process conditions enriching section 100 bar, 60
C
Min diameter enriching section D=0.35 mh =22 m,
vol =2.2 m
3
Packing: Sulzer EX
C. Schacht et al. / J. of Supercritical Fluids 46 (2008) 299321 319
Fig. 35. Draft of the lab scale mixer-settler unit.
Alternatively the production of high purity ethanol (99.5%)
from fermentation broth (710% ethanol) by using supercritical
CO
2
is suggested in the following steps:
(1) Feed of 710% ethanol is fed to a counter current mixer set-
tler unit with 23 stages, operating at 150 bar, 60
C. Ethanol
is enriched to about 7580%.
(2) The extract from the mixer-settler unit is fed to counter cur-
rent packed column operating at 100 bar and 60
C. In this
column, ethanol is concentrated to 99.5% purity.
(3) The rafnate from this packed column contains 6070%
ethanol. It is fed to the mixer settler unit as reux.
The design of the process plant was performed for the treat-
ment of 4000 t/year (resp. 1 t/h) of a feed input of a 7% ethanol
solution. Operating time is 4000 h/year, since for this design a
typical sugar cane processing plant in India with a capacity of
25,000 t/year was used as basis. Hence the distilleries operate at
comparable capacities.
Investment cost for the CC-SFE and mixer settler can be
estimated according delValle et al. [91]. Extraction column has
an inner diameter of 0.3 m, the autoclave volume of the mixer
settler is negligible.
Side product carbon dioxide from fermentation (approxi-
mately 34 kg/h) is equivalent to about 0.5% of the CO
2
cycle,
it may be used to replace the mass losses of the solvent at the
extract and rafnate outlet.
8. Conclusion
Fuel ethanol production from ligno-cellulosic material is not
commercial so far. There is still a wide range of improvements
to be achieved before such a process is competitive to mineral oil
based fuels. SFE technology can contribute at several process
steps advantageously. Several aspects could not be discussed,
e.g. the role of SFE in lignin processing or the role of SCWO in
handling the residues. But it became obvious that only a com-
bination of technologies will be able to achieve the goal. In this
case it is biotechnology and high-pressure technology. There-
fore, the cooperation of experts in these elds seems to be the
most efcient way to overcome certain difculties within this
eld.
Acknowledgements
Numerous co-workers and students contributed to the data
base of this work, as can be seen from the list of references.
In addition, several organisations and companies contributed
over the years: Deutsche Forschungsgemeinschaft (DFG),
Deutsche Bundesstiftung Umwelt (DBU), DSM Vitamins Ltd.
(former F. Hoffmann-La Roche AG).
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