ISSN 00231584, Kinetics and Catalysis, 2013, Vol. 54, No. 3, pp. 344–352. © Pleiades Publishing, Ltd., 2013.

Original Russian Text © B.N. Kuznetsov, V.I. Sharypov, L.I. Grishechko, A. Celzard, 2013, published in Kinetika i Kataliz, 2013, Vol. 54, No. 3, pp. 358–368.

Integrated Catalytic Process for Obtaining Liquid Fuels

from Renewable Lignocellulosic Biomass
B. N. Kuznetsova,b,*, V. I. Sharypova, L. I. Grishechkoa, and A. Celzardc
a
Institute of Chemistry and Chemical Technology, Siberian Branch, Russian Academy of Sciences,
Krasnoyarsk, 660036 Russia
b Siberian Federal University, Krasnoyarsk, 660041 Russia
c
Institut Jean Lamour–UMR CNRS, France
*email: inm@icct.ru
Received February 28, 2012

Abstract—An integrated process for obtaining liquid biofuels is reported. The process is based on the sepa
ration of a lignocellulosic feedstock into cellulose and lowmolecularweight lignin (LMWL) followed by
their conversion into two types of liquid biofuels, namely, hydrocarbon mixtures and bioalcohols. Different
methods of wood fractionation into cellulose and LMWL—mechanical, steam explosion, and selective oxi
dation methods and their combinations—are compared. The amount of cellulose derived from wood and the
amount of hydrolysate obtained from this cellulose for ethanol biosynthesis are determined by the efficiency
of the method used for the fractionation of the lignocellulosic material. The best results are achieved by com
bining mechanical activation and subsequent catalytic oxidation of wood. Use of the resulting highquality
glucose solution, which are free of pentoses—sugars inhibiting ethanol biosynthesis—allows the alcohol
yield to be increased by 30–35%. Liquid hydrocarbon mixtures enriched with phenols and products of their
alkylation with ethanol have been obtained by thermal processing of LMWL in ethanol at an elevated pres
sure.
DOI: 10.1134/S0023158413030105

In recent years, developed countries have been
expressing increasing interest in alternative fuels and
chemical products derived from renewable vegetable
biomass [1–3]. The annual increment of vegetable
biomass on the Earth is 170–200 billion tons on dry
basis, which is equivalent to approximately 70–80 bil
lion tons of petroleum.
Russia accounts for about 23% of the Earth’s for
ests, and approximately 40% of Russia’s forests are in
Siberia. The wood resources include industrial
(mainly coniferous) wood, lowgrade wood (hard
wood), and offgrade (overripe or pest or firedam
aged) wood and wood harvesting and processing waste.
As a whole, these resources provide a reliable raw
material basis for largescale production of chemicals
and alternative fuels from renewable woody biomass.
Coniferous wood and hardwood consist of cellulose
(40–50%), lignin (16–33%), hemicelluloses (15–30%),
extractable substances (5–20%), and inorganic
admixtures [4].
Cellulose is a linear polysaccharide built of glyco
side units С6Н10О5:

OH OH
OH OH
O O HO O O HO
O O O
HO O HO O
OH OH OH OH
OH OH
OH OH
O O HO O O HO
O O O
HO O HO O
OH OH OH OH

Hemicelluloses are branched polysaccharides con Lignin is an aromatic polymer with a branched
structure, Its macromolecules are built from substi
sisting mainly of pentose or hexose units and have tuted hydroxyphenol units interlinked by ether and
shorter chains than cellulose does. carbon–carbon bridges:

344
 INTEGRATED CATALYTIC PROCESS FOR OBTAINING LIQUID FUELS
HOH2C
CH O
Ar O C H
Me
O CH2
HC
HOH2C OMe
HC O
H(C6H10O5)n O CH
The dominant functional groups in lignin are meth
oxyl and phenyl. The hemicellulose and lignin macro
molecules are located between cellulose fibrils and link
them together to form a single rigid structure.
Most of the presentday vegetable biomass process
ing technologies suffer from low productivity and need
high energy inputs and, in some cases, bulky equip
ment. For this reason, researchers are developing new
methods for integrated processing of lowgrade wood
and lignocellulosic waste, focusing on integration of
catalytic processes [5–7]. In particular, an integrated
process was suggested for processing aspen wood. In
this process, wood is subjected to catalytic oxidation
with dioxygen in an alkaline medium to obtain a mix
ture of vanillin, syringaldehyde, and cellulose and the
latter is then converted into levulinic acid by means of
acid catalysis [5]. A catalytic process was also sug
gested for processing of birch wood. It includes the
acidcatalyzed hydrolysis of wood hemicelluloses into
xylose, catalytic oxidation of the lignocellulosic resi
due with dioxygen into vanillin, syringaldehyde, and
cellulose, and acidcatalyzed conversion of cellulose
into levulinic acid [8].
It is expected that, in the near future, the produc
tion of liquid biofuels will be among the largest scale
processes in the processing of renewable lignocellu
losic biomass [9, 10]. The conventional way of con
verting vegetable biomass into liquid hydrocarbon
fuels is biomass pyrolysis yielding resinous liquid, gas
eous, and solid products [11]. Numerous improve
ments to this process allowed the liquid product yield
to be considerably increased [12].
The conversion of vegetable biomass into liquid
products can also be carried out under the action of
molecular hydrogen, synthesis gas, carbon monoxide,
and hydrogendonating organic solvents [13]. As a
rule, the liquid product yield increases as the biomass
KINETICS AND CATALYSIS Vol. 54 No. 3 2013
345
CH2OH OMe
HC OH
CH2
HOH2C
HC
HC O
liquefaction temperature and pressure are raised and
when an appropriate catalyst is employed [14].
Promising integrated processes for converting
lignocellulosic stocks into bioalcohols, hydrocarbon
mixtures, and octane number boosters for motor fuels
include separation of the raw material into cellulose
and lignin and their subsequent conversion into a liq
uid biofuel (Fig. 1).
Below, we will report a study of the main stages of
the integrated conversion of lignocellulosic biomass
into liquid biofuels: catalytic fractionation of biomass
into cellulose and lowmolecularweight lignin
(LMWL); acidcatalyzed conversion of cellulose into
glucose, ethanol, and levulinic acid; thermal dissolu
tion of LMWL in ethanol.
EXPERIMENTAL
The raw material was airdry aspen or birch wood
(2–5 mm fraction), whose chemical composition is
specified in Table 1.
The wood was activated by steam explosion in a
batch reactor [15] at 180–240°С and a saturation
vapor pressure of 1.0–3.3 MPa. The reactor (0.8 L in
volume) was preheated to the preset temperature and
was charged with wood chips. Thereafter, the reactor
was tightly sealed and was filled with steam from a
steam collector. After 3–4 min, the pressure was
abruptly relieved by “shooting” the steamexploded
wood through an open ball valve into a collector. Next,
the wood was subjected to extraction with hot water
(100°С, watertowood ratio of 50) for 3 h in order to
remove watersoluble substances.
Oxidative delignification was carried out in an ace
tic acid–hydrogen peroxide–water–sulfuric acid cat
alyst medium in a stainless steel reactor [13]. The
resulting cellulose was separated from the solution by
346 KUZNETSOV et al.

Lignocellulosic biomass
Chemical separation

Lignin Cellulose

Thermal dissolution Acidcatalyzed

conversions
Liquid Alcohols
hydrocarbons (ethanol, Glucose Levulinic
butanol) acid
Octane number boosters
(alkylbenzenes,
aromatic ethers) Octane number boosters
(esters of levulinic acid)

Fig. 1. Integrated process for conversion of lignocellulosic biomass into alcohols, liquid hydrocarbons, and octane number boosters.

filtration, was washed with distilled water until neutral
pH, and was dried at 103°С.
The residual lignin content of the resulting cellu
lose and the degree of polymerization (DP) were
determined using standard procedures [16].
The structure of the initial and activated woods and
that of the resulting cellulosic products were studied by
scanning electron microscopy (TM1000 microscope,
Hitachi), Xray diffraction, and IR spectroscopy.
Xray diffraction patterns were obtained on a
DRON3M diffractometer (CuKα radiation, 1.54 Å)
in the 2θ range from 5° to 55°. Diffraction peak pro
files were processed using the NewProfile program.
Infrared spectra were recorded on a Vector 22
(Bruker) IR Fourier spectrometer. Spectroscopic data
were processed using the OPUS/YR program (version
2.2). The solid samples (3 mg) were examined as
KBr pellets.
RESULTS AND DISCUSSION
Catalytic Oxidation of Aspen Wood
with Hydrogen Peroxide
Earlier, we suggested a singlestep catalytic cellu
lose production method based on the oxidative delig
nification of various kinds of wood with hydrogen per
oxide, an environmentally friendly chemical, in an
acetic acid–water–catalyst medium [17, 18]. Cellu
lose samples containing <1% residual lignin were
obtained in acceptable yield (44–48 wt %) under opti
mum delignification conditions in the presence of
H2SO4 (2 wt %) and TiO2 (0.5 wt %) catalysts. In the
acetic acid–water–catalyst medium, the oxidative
destruction of lignin and hemicelluloses is accompa
nied by the hydrolysis of the amorphous constituent of
cellulose. This made it possible to develop a single
step method for obtaining microcrystalline cellulose
(MCC) from wood. Note that the industrial technol
ogy of MCC production from wood includes three
stages: wood delignification, bleaching of the cellulo
sic product, and soft acid hydrolysis of the product for
removal of amorphous cellulose [19].
The advantage of the new methods over the con
ventional methods of pure cellulose and MCC pro
duction is that the former consist of a smaller number
of processing steps, need no environmentally hazard
ous sulfur or chlorinecontaining delignifying agents,
and are less exacting toward the quality of the raw
wood. In addition, the LMWL resulting from the oxi
dative delignification of wood is highly reactive, so
there are wider opportunities for its utilization.

Table 1. Chemical composition of raw wood

Content, % of a.d.w. weight

Wood
hemicelluloses extractable
cellulose lignin ash
and uronic acids components

Aspen 46.5 20.4 24.1 4.3 0.5

Silver birch 41.1 19.8 30.1 5.4 0.7

KINETICS AND CATALYSIS Vol. 54 No. 3 2013

 INTEGRATED CATALYTIC PROCESS FOR OBTAINING LIQUID FUELS 347

It is possible to lower the delignification tempera 35

ture and to reduce the consumption of the delignifying
30
agent (hydrogen peroxide) through wood preactiva
tion by steam explosion—shortterm treatment of 25
wood chips with superheated steam followed by abrupt 20

wt %
pressure relief. The wood activation effect is due to two 15
factors, namely, the mechanochemical loosening of 10
wood caused by the abrupt pressure drop and the cat 5
alytic hydrolysis of ether bonds in the lignocellulosic 0
matrix under the action of formic and acetic acids 180 MCC yield
190
resulting from the thermochemical conversion of Steam exp 210 220 230 Lignin content
losion tem
hemicelluloses and sugars in the steam explosion pro perature, °240 of MCC
C
cess [15].
Fig. 2. Steam explosion temperature effect on the MCC
It was investigated how the MCC yield and the yield and on the lignin content of MCC. The processing
residual lignin content of MCC depend on the condi time is 2 min.
tions of steam explosion and on those of the catalytic
oxidative delignification of the steamexploded prod
Cellulose
uct with hydrogen peroxide (temperature, process
duration, component concentrations in the reaction
mixture, fractional composition of the stock). Hydrolysis with Hydrolysis with
a dilute acid at a concentrated acid
The MMC yield from steamexploded aspen wood an elevated temperature at room temperature
was 32.3 to 29.2% of the weight of absolutely dry wood
(a.d.w.) sawdust at a steam explosion temperature of Hydrocellulose Swelling yielding
180–240°С (Fig. 2). As a rule, the resulting MCC a solution of polysaccharides
contained <1 wt % residual lignin. Its content is mini Cellodextrin in the concentrated acid
mized by conducting the steam explosion process at
210–240°С for 2–3 min. As the aspen wood activation Oligosaccharides Dextrins
temperature is raised from 180 to 240°С, the DP of the
resulting MCC decreases from 183 to 83. This DP Cellobiose Oligosaccharides
value is close to the DP of commercial MCC samples,
which is below 250 [19]. It was established by Xray Inversion
diffraction that the supramolecular structure of our
MCC is identical to that of commercial MCC manu DGlucose
factured by Evalar Co. (AnkirB brand).
Fig. 3. Cellulose hydrolysis in dilute and concentrated
mineral acids.
AcidCatalyzed Conversion of Cellulose
The total acid hydrolysis of cellulose to glucose, H+
mC 6 H 12 O 6 reversion
( C 6 H 10 O 5 ) m .
H+
( C 6 H 10 O 5 ) n + nH 2 O nC 6 H 12 O 6 For this reason, cellulose hydrolysis with a concen
Cellulose DGlucose trated acid additionally includes an inversion stage,
yields a number of intermediate products, with DP specifically, dilution of the reaction mixture with water
decreasing progressively. Cellulose hydrolysis under to an acid concentration of 3–4% and boiling:
the action of dilute and concentrated acids occurs via H+
different pathways and under different conditions ( C 6 H 10 O 5 ) m + mH 2 O inversion at 100°C
mC 6 H 2 O 6 .
(Fig. 3). Cellulose hydrolysis with concentrated acids
At the early stages of hightemperature hydrolysis affords a higher monosaccharide yield than hydrolysis
by a dilute acid, cellulose loses its fibrous structure and with dilute acids; however, it is rather difficult to
turns into hydrocellulose, which is a mixture of cellu ensure reuse of the concentrated acids.
lose and the hydrolysis products of its amorphous con The industrial technologies used to produce glu
stituent. Hydrocellulose hydrolyzes less rapidly, cosecontaining hydrolysates are based on the high
because it has a higher degree of crystallinity than the temperature catalytic hydrolysis of a lignocellulosic
initial cellulose. stock (wood, agricultural waste) with dilute sulfuric or
The monosaccharides resulting from cellulose hydrochloric acid [20]. The resulting hydrolysates are
hydrolysis with a concentrated acid partially undergo contaminated by the destruction products of lignin
reversion (reaction opposite to hydrolysis), yielding and hemicelluloses and by the products of secondary
oligosaccharides and lowmolecular weight dextrins: reactions of monosaccharides and other hydrolysis

KINETICS AND CATALYSIS Vol. 54 No. 3 2013

348 KUZNETSOV et al.

Lignocellulosic biomass 10–11, and a process duration of 2–3 h afforded

hydrolysates containing up to 360 µg/mL of pentoses,
Hydrolytic Hydrolysis with Partially Prehydrolysis and their yield was up to 10 wt %. Use of 2% HCl as the
lignin
70% H2SO4 hydrolyzed 2% HCl or catalyst raises the pentose content to 795 µg/mL and
and inversion biomass H2SO4 the pentose yield to 14.2 wt %.
C6 sugars C5 sugars In order to optimize the processing condition for
glucose production from prehydrolyzed wood, we
Fig. 4. Fractionation of lignocellulosic biomass into C6 studied the effect of temperature, liquortowood
and C5 sugars and hydrolytic lignin. ratio, hydrolysis time, and H2SO4 concentration on
the hexose and pentose contents of the hydrolysate.
The highest concentration of reducing substances
35 (27%) was achieved via the hydrolysis of the solid res
Yield, % of a.d.w. weight

30
25
20
15
10
5 in bioethanol synthesis.
0 For obtaining pentosefree glucose solutions, it was
30 60 90 120 150 180 210
Prehydrolysis time, min
Fig. 5. Prehydrolysis time effect on the hydrolysate yield
from birch wood at a liquortowood ratio of 10, 98°С, and
H2SO4 catalyst concentrations of (1) 2 and (2) 3 wt %.
intermediates. This necessitates use of additional puri
fication stages for obtaining glucose or for further bio
chemical conversion of the hydrolysate into bioalco
hols and other valuable products.
The yeast used in the enzymatic synthesis of etha
nol can assimilate only hexose sugars, while pentose
sugars inhibit the process. It is, therefore, necessary to
remove the pentosancontaining hemicelluloses from
lignocellulosic biomass for increasing the ethanol
yield.
The hemicelluloses are removed almost entirely by
the twostep acidcatalyzed hydrolysis of the lignocel
lulosic stock (Fig. 4).
By investigating the soft acid hydrolysis (prehydrol
ysis) of birch wood and its subsequent total hydrolysis,
we determined the composition of the hydrolysates
and found the prehydrolysis conditions maximizing
the С5 sugar content. In the hydrolysis of birch wood
with 2–3% H2SO4 at 98°С for 2–3 h, the hydrolysate
yield was 20–28% of the a.d.w. weight (Fig. 5). The
prehydrolysis of birch sawdust in the presence of 2–
5% sulfuric acid at 98°С, a liquortowood ratio of
2
idue with 75% H2SO4 at a liquortowood ratio of 5.5
1 and a reaction time of 3 h. Under these conditions, the
hexose content of the hydrolysate was 581 µg/mL,
which is equal to 15.7% of the a.d.w. weight. The high
pentose concentration in this hydrolysate (3.9%)
causes problems in subsequent use of the hydrolysate
240 270 suggested to introduce an additional processing
step—catalytic delignification of prehydrolyzed birch
wood in an acetic acid medium (23.6–25.8%) in the
presence of Н2О2 (4.2–6.4%) and H2SO4 (2%) at
120°С, a liquortowood ratio of 10, and a processing
time of 3 h. A cellulosic product containing 76% cel
lulose and 3.2% residual lignin was obtained under
these conditions, and the yield of this product was 55%
of the weight of absolutely dry prehydrolyzed wood.
The hydrolysis of the cellulosic product with 75%
H2SO4 at 23°С, a liquortowood ratio of 5.5, and a
reaction time of 1 h followed by inversion produced
hexoses almost free of С5 sugars in 26.6 wt % yield.
In the case of aspen wood, hemicelluloses are also
removed by shortterm treatment of the wood with
superheated steam under steam explosion conditions
(Fig. 6).
The absence of С5 sugars (which inhibit the fer
mentation of glucose into ethanol) in the hydrolysate
allows the yield of bioethanol from wood to be
increased by 30–35%.
Another valuable product of the acidcatalyzed
depolymerization of cellulose is levulinic acid. This
product is among the most important compounds
derived from renewable biomass and provides a basis
for the synthesis of numerous chemicals and motor
fuel components [21].
Levulinic acid forms from cellulose via the follow
ing acidcatalyzed reactions:

O CHO H3C COOH

(C6H10O5)n nC6H10O6 HO
O
Cellulose Glucose 5Hydroxymethylfurfural Levulinic acid

The investigation of the acidcatalyzed synthesis of levulinic acid by steam conversion of wood and cellu

KINETICS AND CATALYSIS Vol. 54 No. 3 2013

 INTEGRATED CATALYTIC PROCESS FOR OBTAINING LIQUID FUELS 349

lose in a digestertype reactor demonstrated that the 25

yield of the acid is determined by the processing tem

Content, % of a.d.w. weight

perature and duration and by the nature of the catalyst. 20
The highest yield of levulinic acid from wood (about
24%) was attained in the presence of Н2SO4 (5 wt %) 15
as the catalyst at 220°С and a process duration of
about 2 h. Varying the kind of wood (aspen, pine, fir,
10
birch) changed the product yield only slightly.
In the steam conversion of cellulose impregnated 5
with H2SO4, the highest yield of levulinic acid at
240°С was about 35–40 wt % (Fig. 7). 0
The acidcatalyzed conversions of carbohydrates 0 1.0 1.5 2.0 2.5 3.0
(fructose, glucose, and saccharose) at moderate tem Processing time, min
peratures (about 100°С) lead to the formation of Fig. 6. Hemicellulose content of the solid products of the
levulinic acid from monosaccharides and disaccha steam explosion of aspen wood at 220°С.
rides at a fairly high rate and in high yield [22]. The
inorganic acids that catalyze carbohydrate conversion
into levulinic acid can be arranged in the following Levulinic
order according to their activity: HCl > H2SO4 > acid yield, %
H3PO4 [18].
45
A promising largescale application of levulinic
40
acid is the synthesis of octane number boosters for
35
motor fuels and the solvent methyltetrahydrofuran
(MTHF) [23, 24]. The new, singlestep, catalytic 30
levulinic acidtoMTHF conversion process devel 25
oped by Pacific Northwest National Laboratory 20
affords the target product in 49 wt % yield (66% of the 15 240

°С
theoretical value). 10 230

e,
5

tur
220

era
0
Thermal Conversion of Lignin 2

mp
4 210
6

into Liquid Hydrocarbons
Lignin is converted into liquid hydrocarbon mix
tures by various methods based on pyrolysis, hydropy
rolysis, hydrogenation, acid–base conversion, and
thermal dissolution [25]. The reductive destruction of
lignin yields substituted phenols and benzenes and
other aromatic compounds.
Efficient liquefaction of hydrolytic lignin was
achieved by employing lowboiling alcohols, such as
propanol and ethanol. Lignin is unreadily soluble in
methanol; however, its liquefaction efficiency is much
higher in the presence of a catalyst. A strong catalytic
effect is exerted by the zinc–chromium and iron–
zinc–chromium compositions that accelerate the
methanol synthesis and decomposition reactions [13].
The lignin conversion in their presence is higher by a
factor of 3–5.
If a liquid biofuel derived from lignin contains
much oxygen, it will have a reduced calorific value.
The high corrosive activity of these biofuels, which is
due to the presence of phenols and lowmolecular
weight organic acids (mainly acetic and formic acids),
prevents them from being used in internalcombustion
engines.
For motor fuel production from lignin, it is neces
sary to carry out the hydrorefining of the liquid prod
ucts of lignin conversion. This can be done using con
Te
Time, 8
h 10
Fig. 7. Levulinic acid yield in cellulose conversion in the
presence of 5% Н2SO4.
ventional oil hydrotreating and cracking catalysts [26].
The most efficient ones are bifunctional catalysts con
taining components intended both for hydrotreating
(metals, sulfides) and for hydrocracking (zeolites, alu
minosilicates).
There is information that it is possible to combine
lignin depolymerization with the refining of the result
ing liquid products for obtaining motor fuel compo
nents. Twostage lignin conversion processes were
adapted to the production of two types of octane num
ber boosters, namely, С7–С10 alkylbenzenes and aryl
methyl ethers (aryl = phenyl, methylphenyl, or dime
thylphenyl) [27].
Alkylated phenol + aliphatic hydrocarbon mixtures
were obtained in 60 to 95% yield by lignin solvolysis
with ethanol or propanol mixed with formic acid [28].
Aromatic hydrocarbons were synthesized from
acetonesoluble Alcell lignin over the HZSM catalyst
[29]. The highest yield of liquid products (43 wt %)
was observed at a lignin conversion temperature of
550°С and an acetone–lignin mixture (2 : 1 w/w)

KINETICS AND CATALYSIS Vol. 54 No. 3 2013

350 KUZNETSOV et al.

% The thermoanalytical data for the thermal decom

70
60 1
1 into consideration the composition of the released
50
1
40
30 4 3
3 3
20
2 2 4 2
10
0 resulting in a weight loss of 16. The reactivity of aspen
Acetic acid Alkali Sulfuric acid
Fig. 8. Effect of the method of lignin separation from aspen
wood on the results of the thermal dissolution of lignin in
ethanol at 400°С and a pressure of 5 MPa: (1) conversion,
(2) yield of liquid products with bp > 180°С, (3) yield of
liquid products with bp < 180°С, and (4) gas yield.
space velocity of 5 h–1. The liquid product was domi
nated by aromatic hydrocarbons, including toluene
(36.7 wt %) and benzene (9.4 wt %), and by xyloses
(33.0 wt %).
Tetraethyllead as an additive raising the octane
number of gasoline is now widely replaced with
organic antiknock agents. Promising ones are cresol,
alkyl ethers of phenol, and other compounds present
in the phenol fraction of wood oil. These phenolic
compounds are also used in the synthesis of antioxi
dants (naphthols, cresols, and other alkylsubstituted
phenols capable of scavenging free radicals).
We studied the composition and thermal conver
sion of the lignins isolated from aspen wood by the
alkali, sulfuric acid, and acetic acid methods. Accord
ing to IR spectroscopic data, acetic acid lignin (С,
63.7%; О, 33.0%; Н, 5.2%) has an increased carboxyl
group content, while sulfuric acid lignin (С, 64.6%;
О, 30.4%; Н, 5.2%) is richer in aromatic structures.
position of lignin indicated two decomposition rate
peaks in the 250–311 and 364–407°С ranges. Taking
gaseous products, we hypothesized that the first peak is
due to the breaking of thermally less stable oxygen
involving bonds and the second peak arises from the
breakdown of the main lignin structure with the cleav
age of both oxygeninvolving and C–C bonds. The
4 first stage makes the most significant contribution to
the thermal decomposition of acetic acid lignin,
wood lignin in thermal dissolution in alcohols depends
considerably on the method by which the lignin was
separated from the wood (Fig. 8).The maximum con
version (57.2–57.6 wt %) was observed in the decom
position of acetic acid lignin; the highest yield of liquid
products with bp < 180°С (26.0–28.5 wt %), in the
thermolysis of alkali lignin.
The boiling point of the greater part of the resulting
products increases in the following lignin order: alkali <
acetic acid < sulfuric acid. The composition of the
liquid pyrolysis products for the different lignins,
determined by the GC–MS method, is presented in
Table 2.
The pyrolysis products of organosolv lignin are rich
in acyclic oxygencontaining compounds, mainly eth
anol and acetic acid. The liquid pyrolysis products of
hydrolytic lignin contain large amounts of phenol
derivatives; in particular, their 2methoxyphenol con
tent is higher than 24 wt %. The decomposition prod
ucts of alkali lignin include the following phenols: 2,6
dimethoxyphenol (12 wt %), 4ethylphenol (7 wt %),
2,6dimethoxy4(2propenyl)phenol (4 wt %),
2methoxyphenol (7 wt %), and 2methoxy4eth
ylphenol (4 wt %).

Table 2. Composition of the liquid products of the thermal conversion of lignin in ethanol (in percent of the total area of
all peaks)

Lignin type
Compound
sulfuric acid acetic acid alkali

Phenol 9.1 3.9 17.4

Phenol derivatives: 56.3 53.1 25.6
ethylphenols 26.7 30.1 15.9
propylphenols 1.2 1.6 1.3
Alkylbenzenes 5.1 3.4 4.1
Acids 7.0 1.7 20.1
Hydrocarbons 2.3 5.6 8.7

KINETICS AND CATALYSIS Vol. 54 No. 3 2013

 INTEGRATED CATALYTIC PROCESS FOR OBTAINING LIQUID FUELS
CONCLUSIONS
Above, we considered the promising avenues of
improving the integrated process for producing liquid
hydrocarbon and alcohol fuels from renewable cellu
losic raw materials, namely, wood and agricultural
waste. A specific feature of the process is the prelimi
nary separation of lignocellulosic biomass into cellu
lose and lignin and their subsequent processing in a
single technological cycle to obtain two types of liquid
biofuels: hydrocarbon mixtures and alcohols.
It was investigated whether it is possible to opti
mize the following separate stages of the integrated
process: catalytic fractionation of biomass into cellu
lose and lowmolecularweight lignin, acidcatalyzed
cellulose depolymerization into glucose (for subse
quent bioethanol synthesis) and levulinic acid, and
thermal dissolution of lowmolecularweight lignin in
ethanol for obtaining liquid hydrocarbons.
Almost complete separation of wood into polysac
charides and lignin is achieved by catalytic wood oxi
dation with hydrogen peroxide in the acetic acid–
water medium. Varying the processing temperature,
the concentrations of hydrogen peroxide, acetic acid,
and catalyst (H2SO4, TiO2), the liquortowood ratio,
and process duration provides means to control the
composition of the resulting cellulose and lowmolec
ularweight lignin. Under the optimum catalytic wood
oxidation conditions, it is possible to obtain cellulose
almost free of residual lignin.
For fractionation of hemicelluloserich wood, it is
appropriate to combine the soft acid hydrolysis (pre
hydrolysis) stage and the catalytic oxidation of the
prehydrolyzed wood with hydrogen peroxide. The
prehydrolysis stage yields С5 sugars, and the oxidation
of the prehydrolyzed wood affords microcrystalline
cellulose and lowmolecularweight lignin.
The most efficient fractionation of wood into cel
lulose and lignin is achieved by combining wood acti
vation by steam explosion with the catalytic oxidation
of the product. The removal of hemicelluloses at the
steam explosion stage makes it possible to obtain
microcrystalline cellulose, whose acidcatalyzed
hydrolysis yields glucose solutions containing no С5
sugars, which are inhibitors of ethanol biosynthesis.
Another highly demanded product of acidcata
lyzed cellulose conversion is levulinic acid. It can be
synthesized in rather high yield (up to 40 wt %) by
treating, with superheated steam at 240°С, cellulose
impregnated with 5% H2SO4. The conversion of glu
cose into levulinic acid can be carried out at about
100°С in the presence of dilute inorganic acids.
The lowmolecularweight lignin resulting from
the fractionation of lignocellulosic biomass by cata
lytic oxidation is processed by its dissolution in etha
nol derived from the cellulosic constituent of raw
wood. The hydrocarbon mixtures obtained in this way
contain octane number boosters for motor fuels (alky
lbenzenes, phenol ethers, etc.).
KINETICS AND CATALYSIS Vol. 54 No. 3 2013
351
Further improvement of the integrated process for
conversion of the lignocellulosic stock into bioethanol
and octanenumber boosters needs development of
more efficient catalysts for the oxidative depolymer
ization of biomass, avidcatalyzed depolymerization
of cellulose, and thermal dissolution of lignin in alco
hols.
In recent years, there have been extensive studies of
solid acidic and bifunctional catalysts capable of
effecting cellulose hydrolysis into glucose and lignin
conversion into octane number boosters for motor
fuels [30]. For this purpose, it is promising to employ
nanostructured catalysts based on carbon, oxide, and
carbon–mineral porous materials [31].
Since cellulose hydrolysis is carried out in aqueous
media, the solid catalyst to be used should be resistant
to water and its surface should have optimum hydro
philic/hydrophobic properties.
Search for optimum catalysts for the heteroge
neous catalytic conversion of lignin is facilitated by the
fact that the process takes place in hydrocarbon media
and allows use of solid acidic and bifunctional cata
lysts employed in petrochemical process.
ACKNOWLEDGMENTS
This work was supported in part by the Presidium of
the Russian Academy of Sciences through the pro
gram “Chemical Aspects of Power Engineering”
(project no. 3.8) and by the ARCUS program (project
“Lotharingia–Russia 2”).
REFERENCES
1. Feedstocks for the Future, ACS Symposium Series,
vol. 921, Washington, DC: American Chemical Society,
2006.
2. Biorefineries—Industrial Processes and Products,
Kamm, B., Gruber, P.R., and Kamm, M., Eds., Wein
heim: VCH, 2006.
3. Kuznetsov, B.N., Khim. Interes. Ust. Razv., 2011,
vol. 19, p. 77.
4. Fengel, D. and Wegener, G., Wood: Chemistry, Ultra
structure, Reactions, Berlin: Gruyter, 1984.
5. Kuznetsov, B.N., Kuznetsova, S.A., and Taraban’ko, V.E.,
Ross. Khim. Zh., 2004, vol. 48, no. 3, p. 4.
6. Gallezot, P., Catal. Today, 2007, vol. 121, p. 76.
7. SerranoRuiz, J.C. and Dumesic, J.A., Energy Environ.
Sci., 2011, vol. 4, p. 83.
8. Kuznetsov, B.N., Kuznetsova, S.A., Danilov, V.G., and
Taraban’ko, V.E., Khim. Interes. Ust. Razv., 2005,
vol. 13, p. 655.
9. Klass, D.L., Biomass for Renewable Energy, Fuels and
Chemicals, San Diego: Academic, 1998.
10. Kuznetsov, B.N., Ross. Khim. Zh., 2003, vol. 47, no. 6,
p. 83.
11. Biomass Pyrolysis Liquids Upgrading and Utilization,
Bridgwater, A.V. and Grassi, G., Eds., London: Elsevier,
1990.
352 KUZNETSOV et al.
12. Bridgwater, A.V., Thermal Biomass Conversion and Utili
zation: Biomass Information System, published by the
European Commission, EUR 16863, 1996.
13. Kuznetsov, B.N., Sharypov, V.I., Kuznetsova, S.A.,
Taraban’ko, V.E., and Ivanchenko, N.M., Int. J. Hydro
gen Energy, 2009, vol. 34, p. 7057.
14. Kuznetsov, B.N., Kataliz khimicheskikh prevrashchenii
uglya i biomassy (Catalysis in Chemical Conversions of
Coal and Biomass), Novosibirsk: Nauka, 1990.
15. Kuznetsova, S.A., Aleksandrova, N.B., and Kuzne
tsov, B.N., Khim. Interes. Ust. Razv., 2001, vol. 9, p. 655.
16. Obolenskaya, A.V., El’nitskaya, Z.P., and Leono
vich, A.A., Laboratornye raboty po khimii drevesiny i
tsellyulozy (Wood and Cellulose Chemistry: A Lab
Course), Moscow: Ekologiya, 1991.
17. Kuznetsov, B.N., Danilov, V.G., Kozlov, I.A., Tara
ban’ko, V.E., Ivanchenko, N.M., and Alexand
rova, N.B., Catal. Today, 2002, vol. 75, p. 211.
18. Kuznetsov, B.N., Taraban’ko, V.E., and Kuzne
tsova, S.A., Kinet. Catal., 2008, vol. 49, no. 4, p. 517.
19. Petropavlovskii, G.A. and Kotel’nikova, N.E., Khim.
Drev., 1979, no. 6, p. 3.
20. Khol’kin, A.I., Tekhnologiya gidroliznykh proizvodstv
(Hydrolysis Technology), Moscow: Lesnaya Promy
shlennoct’, 1989.
21. Rackemann, D.W. and Doherty, W.O.S., Biofuels, Bio
prod. Biorefin., 2011, vol. 5, no. 2, p. 198.
doi: 10.1002/bbb
22. Taraban’ko, V.E., Chernyak, M.Yu., Aralova, S.V., and
Kuznetsov, B.N., React. Kinet. Catal. Lett., 2002, vol. 75,
no. 1, p. 117.
23. Huber, G. and Dumesic, J.A., Catal. Today, 2006,
vol. 111, p. 119.
24. RomanLeshkov, Y., Barrett, C.J., Liu, Z.Y., and
Dumesic, J.A., Nature, 2007, vol. 447, p. 982.
25. Zakzeski, J., Bruijnincx, P.C.A., Jongerius, A.L., and
Weckhuysen, B.M., Chem. Rev., 2010, vol. 110, p. 3552.
26. Elliot, D.C., Energy Fuels, 2007, vol. 21, p. 1792.
27. Shabtai, J., Zmierczak, W., and Chornet, E., Proc. 3rd
Biomass Conf. of the Americas, Montreal, 1997, vol. 2,
p. 1037.
28. Kleinert, N. and Barth, T., Chem. Technol., 2008,
vol. 31, no. 5, p. 736.
29. Thring, R.W., Katikaneni, S.P.R., and Bakhshi, N.N.,
Fuel Process. Technol., 2000, vol. 65, p. 17.
30. Rinidi, R. and Schuth, F., Energy Environ. Sci., 2009,
vol. 2, p. 610.
31. Shiju, N.R. and Guliants, V.V., Appl. Catal., A, 2009,
vol. 356, p. 1.
Translated by D. Zvukov
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