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ru
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DESIGN OF CATALYTIC PROCESSES FOR
BIOFUELS PRODUCTION
III
RUSNANOTECH 2010
Vadim A. Yakovlev
Valentin N. Parmon
Boreskov Institute of Catalysis
Novosibirsk, Russia
yakovlev@catalysis.ru
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Contents of the Presentation
I. Situation in World concerning renewable and local fuel
sources
II. The innovative catalytic ways of biomass processing for the
energetics within international projects and perspective
directions
II.I. Biofuels from wood
II.II. Improved technology of biodiesel production
II.III. Green diesel production
II.IV. Other perspective directions of biofuels production
III. Answer to a question: Can biomass replace fossil oil and
natural gas as feed stock for motor fuels production or not?
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Source: IEA, WEO, Reference scenario, 2002 and 2007.
The present energy model is based on ever-increasing demand and
the perpetuation of fossil fuels
Mtoe = Million tons of oil equivalent
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Shell international BV, Shell energy scenarios to 2050. 2008
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Present problems of biomass processing into fuels and
energy:
At present biofuels have higher first cost than fossil oil-
fuels and natural gas
The main reasons:
1. High costs of farming, harvest, transport of biomass
2. Lower technological level of biomass processing in
comparison with oil refining
On the whole now the situation in bioenergetics is
similar to the one with oil-refining 90-100 years ago.
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Source: New Energy Finance
Bioenergy Technology Pathways
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Biofuel pathway costs
Roberto Rodriguez Labastida, BTL investment trends and levelled costs of production, Bloomberg New
Energy Finance (2010).
Note: The final biofuel product from each pathway, and its associated conversion cost, has been
compared with the energy content of a litre of gasoline.
- Feedstock Cost - Conversation Cost - Capital Cost
Gasoline
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Contents of the Presentation
I. Situation in World concerning renewable and local fuel
sources
II. The innovative catalytic ways of biomass processing for the
energetics within international projects and perspective
directions
II.I. Biofuels from wood
II.II. Improved technology of biodiesel production
II.III. Green diesel production
II.IV. Other perspective directions of biofuels production
III. Answer to a question: Can biomass replace fossil oil and
natural gas as feed stock for motor fuels production or not?
www.catalysis.ru
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Biomass
Pyrolysis
plant
Biomass
Pyrolysis
plant
Biomass
Pyrolysis
plant
Standard
Refinery
Upgrader
Biomass
Pyrolysis
plant
Transportation fuels
Chemicals
Heat and power
Schematic representation of the biomass-pyrolysis-upgrading-refinery concept
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Fractionation
during and
after
condensation
Biomass
residues
Co-processing in
conventional
petroleum refinery
De-oxygenation
Hydrocarbon-rich fraction
Lignin-rich
fraction
Conversion
Derivatives of hemicelluloses
and celluloses
Conventional fuels
and chemicals
Liquefaction
Note: hydrocarbon-rich fractions are formed when the biomass feedstock contains a
significant amount of extractive substances; e.g the case for forestry residues.
Energy
production
Process
residues
Oxygenated products
(blending)
role of BIC
Netherlands BTG, University of Twente, Shell Global Solutions
International, University of Groningen, Albemarle Catalysts Co.
Finland VTT, Helsinki University of Technology
France CNRS-IRC, ALMA Consulting Group, Metabolic Explorer
Germany - Ineos-Phenolics, UHDE, Institute of Wood Chemistry Hamburg
United Kingdom - Johnson Matthey
Sweden - STFI-PACKFORSK
Slovenia - Slovenian Institute of Chemistry
Russia - Boreskov Institute of Catalysis
List of BIOCOUP project participants
Tasks of BIC within the project
Development of bio-oil deoxygenation catalysts
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What is bio-oil?
Liquid (bio-oil)
Upgraded biocrudeoil
HDO
H
2
catalysts
up to 70 mass %
to dry biomass
Dry Biomass
Flash pyrolysis
T > 450
0
C, t < 1 s,
heating rates > 1000
0
C
The main disadvantages of bio-oil:
Very viscous
Unstable (readily polymerized)
Poorly evaporated
Immiscible with ordinary fuels
Strongly acidic (=3)
Because of high content of oxygen
C 30-60 %
30-60 %
H 6 - 7 %
N <1 %
Up to 30 % of H
2
O
Elemental composition:
so, bio-oil has to be upgraded in order to
improve its quality as a fuel
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LMM Lignin:
Catechols, lignine
derived phenols and
guaiacols (~ 13%)
OH
R
OH
R
Acids (~4%)
C R
O
OH
C R
O
OH
C
O
HO
Aldehydes,
Ketones, Alcohols
( ~ 15%)
Sugars (~34%)
HMM Lignin (~ 2%)
dehydration ( H
2
O)
hydrogenolysis ( H
2
O)
decarbonylation ( CO)
decarboxylation ( CO
2
)
decarboxylation ( CO
2
)

cat
T

cat
T, H
2

cat
T, CO

cat
T

cat
T
Upgrading of Bio--Crude--Oil via Catalytic Deoxygenation
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Hydrodeoxygenation catalysts development
as key step of HDO process development
Traditional catalysts for
hydrodeoxygenation (HDO):
1. Sulfided Ni-Mo/Al
2
O
3
, Co-Mo/Al
2
O
3
2. Pd, Pd-Pt, Rh-based catalysts
These catalysts dont fit
for bio-oil upgrading:
- Noble catalysts are very
expensive for large-scale
processes
- Sulfided catalysts are
deactivated in target process
Prices of HDO catalysts active metal
from the year 1996 to 2010.
Conclusion: catalysts have to be cheaper and non-sulfided
Rh $2250
Pt $1703
Pd $625
Ru $178
Ni $ 0,62
1996 1998 2000 2002 2004 2006 2008 2010
0
2000
4000
6000
8000
10000

Rh, Pt, Pd, Ni - http://www.kitco.com
Ru - http://www.platinum.matthey.com
U
S
$

/

T
r
o
y

o
n
c
e
Year
Rh
Pt
Pd
Ru
Ni
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Catalysts screening
Active metal Support
Ni-Mo, Co-Mo sulf.,
Ni-Mo, Co-Mo ox.,
Ni-Mo-Mn, Ni-Mo-Mg,
Rh, Pd, Pt, Rh-Co, Ni,
Co, Cu, Ni-Cu, Co-Cu,
Fe-Cu
Al
2
O
3
, SiO
2
, C-SiO
2
, Al
2
O
3
- SiO
2
, Cr
2
O
3
,
CeO
2
, ZrO
2
, CoSiO
3
Step 1: Screening of HDO catalysts
Catalysts
Rh/CoSiO
3
Rh/ZrO
2
Rh/ CeO
2
LHSV, h
-1
0,5 1,0 0,4
Anisole conversion (%) 82,0 99,6 99,9
HDO degree (%) 79,2 90,8 94,3
HDO tests results:
Catalysts
RhCo/Al
2
O
3
Rh/SiO
2
RhCo/SiO
2
LHSV, h
-1
0,3 0,3 0,3
Anisole conversion (%) 98,2 53,4 99,0
HDO degree (%) 74,7 30,3 81,1
Reaction conditions:
Substrate: anisole
Temperature: 300
o
C
Pressure
H2
: 0,5 MPa
LHSV: 6 h
-1
Reactor type: flow fixed-bed
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Catalysts screening and comparison with the commercial catalysts
Catalyst
S/Ni-Mo/Al
2
O
3
(Albemarle)
IC3-47
(BIC)
Ni/ Cr
2
O
3
(Chirchik)
Rh/CoSiO
(BIC)
H
2
pressure, MPa 0,5 0,5 0,5 0,5
Temperature,
0
C 300 300 300 300
LHSV, h
-1
0,6 6 6 0,5
Conversion, % 92,8 78,6 90,2
82,0
HDO degree, % 15,4 95,9 15,7
79,2
% 100
'
=

i
i
i
i
C
C
HDO
i
C'
i
C
HDO degree corresponds to the selectivity of hydrogenated products formation:
- the concentration of oxygen-free i product
- the concentration of i product
Ni/ Cr
2
O
3
Benzene hydrogenation into
cyclohexane
S/Ni-Mo/Al
2
O
3
Oil hydrotreating
Step 2: Ni-based catalysts
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Catalysts screening and comparison with the commercial catalysts
Catalyst
S/Ni-Mo/Al
2
O
3
(Albemarle)
IC-3-47
(BIC)
Ni/ Cr
2
O
3
(Chirchik)
Products
selectivity, %
cyclohexane 8,5 24,3 9,5
benzene 6,2 59,9 6,2
toluene 1,9 2,9 0
phenoles 70,3 0 0
cyclohexanole 0 2,3 81,7
cyclohexanone 0 1,8 2,6
other products 13,1 2,9 0
OH
OH
desired
product
Step 2: Ni-based catalysts
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System NiCu/ Al
2
O
3
Catalyst
metal, % wt.
support
Cu Ni
24.5Cu 24,50 - Al
2
O
3
5.92Ni18.2Cu 18,20 5,92 Al
2
O
3
13.3Ni11.8Cu 11,80 13,30 Al
2
O
3
13.8Ni6.83Cu 6,83 13,80 Al
2
O
3
16Ni2Cu 2,00 16,00 Al
2
O
3
20.8Ni -- 20,80 Al
2
O
3
Catalyst conversion,% HDO, %
Quartz 2,8 0
Al
2
O
3
11,8 0
24.5Cu 95,3 1,0
5.92Ni18.2Cu 76,9 72,8
13.3Ni11.8Cu 70,3 82,8
13.8Ni6.83Cu 73,8 90,6
16Ni2Cu 78,6 95,9
20.8Ni 66,1 97,8
HDO tests results:
Cu loading into nickel on alumina catalysts increases
the selectivity of hydrogenated aliphatic products
(cyclohexane, methylcyclohexane) formation against
the aromatic products (benzene, toluene)
Spec.cat.activity
molh
-1
g
-1

0,66
0,30
0,34
0,33
0,22
Step 3: Optimization of Ni-Cu catalysts composition
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In-situ XRD analysis of NiCu/ Al
2
O
3
system
(under the hydrogen atmosphere, heating up to 300

)
Support (o-Al
2
O
3
) lattice parameter vs. Ni content
(%, wt.) in the catalyst
Ni ions diffuse into the alumina structure with
formation of the solid solution
Lattice parameter of metallic nickel differs
from the PDF card value
Formation of the solid solution Ni
1-x
Cu
x
Step 3: Optimization of Ni-Cu catalysts composition
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System NiCu/ Al
2
O
3
TPR analysis
(thermo-programmed reduction)
1. The presence of copper
promotes the nickel oxide
reduction at a lower
temperatures.
2. The addition of copper
into Ni/Al
2
O
3
promotes
the decrease of the
surface Ni Al solid
solution content in the
samples.
Step 3: Optimization of Ni-Cu catalysts composition
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Conception of bifunctional nature of HDO catalysts
First type (I) of active component hydrogen activation
(noble metals, nickel, cupper et al.)
Second type (II) of active component oxy-organic activation
(transfer metals in reduced or oxidized forms with variable valence at
HDO reaction conditions)
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48MGeneral Assembly
38
RUG-Results Highlight
Exploratory Catalyst Screening
Pyrolysis oil, 350
o
C, 200 bar H
2
, 4 h. Catalysts provided by BIC/TKK/ALBE
NiCu catalysts are potential for further development
0.00
10.00
20.00
30.00
40.00
50.00
60.00
P
i
n
e
o
i
l
R
u
/
C
5
w
t
%
R
u
/
C
3
.
3
3
w
t
%
R
u
/
C
2
w
t
%
+
a
c
t
P
d
/
C
P
d
P
t
/
S
i
O
2
-
A
l
2
O
3
(
A
lb
e
)
R
h
/
C
e
O
2
R
h
/
Z
r
O
2
R
h
/
C
o
S
iO
3
R
h
/
Z
r
O
2
R
h
P
d
/
Z
r
O
2
R
h
P
t
/
Z
r
O
2
P
d
/
Z
r
O
2
P
d
P
t
/
Z
r
O
2
P
t
/
Z
r
O
2
N
i
C
u
/
A
l
2
O
3
F
e
C
u
/
A
l
2
O
3
N
i
C
u
/
Z
r
O
2
N
i
C
u
/
C
e
O
2
(
c
o
)
N
i
C
u
/
C
e
O
2
(
w
e
t
)
N
i
C
u
/
C
N
i
C
u
/
C
e
O
2
-
Z
r
O
2
c
r
a
c
k
i
n
g
(
N
i
C
u
/
d
-
A
l
2
O
3
)
c
r
a
c
k
+
N
i
C
u
/
C
e
O
2
-
Z
r
O
2
N
i
C
u
/
s
i
b
u
n
i
t
e
N
i
C
u
/
C
e
O
2
Catalyst
O
x
y
g
e
n
c
o
n
t
e
n
t
(
w
t
-
%
)
noble metals
cheaper transition metals
:
flowable products at RT
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Contents of the Presentation
I. Situation in World concerning renewable and local fuel
sources
II. The innovative catalytic ways of biomass processing for the
energetics within international projects and perspective
directions
II.I. Biofuels from wood
II.II. Improved technology of biodiesel production
II.III. Green diesel production
II.IV. Other perspective directions of biofuels production
III. Answer to a question: Can biomass replace fossil oil and
natural gas as feed stock for motor fuels production or not?
www.catalysis.ru
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Problems:
- Low quality of biodiesel
- a lot of waste at the production
1. Improved Technology of Biodiesel Production
Application:
as additives (5-20%) to traditional diesel
Plant oils + Methanol Glycerine + Biodiesel
Homogeneous
catalyst
H
2
SO
4
or
NaOH
Traditional technology:
Manufacture of biodiesel:
more than 12 million tons in 2009
Prediction:
biodiesel production growth ~10-15% per year
O
O H
2
C
O
O
HC
O
O H
2
C
R
1
R
2
R
3
CH
3
OH
OH H
2
C
OH HC
OH H
2
C
O
O H
3
C
R
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Why heterogeneous catalysts?
1. Cleaner process
2. Zero soap production
3. Recovery of the catalysts is reusable
4. Cleaner Biodiesel
5. Cleaner Glycerol (99% against 75-80%)
Affordability:
reduction of process cost
2 - 2,1 times
heterogeneous systems
dont form soap during the reaction,
reduce the generation of effluents, no corrosion,
simplify the purification of by products,
facilitate the separation of biodiesel from the reaction media
and also allow the recovery of the catalyst by filtration,
allow regenerate the catalysts by washing with solvents,
oxidation or thermo treatment,
purity of the glycerinic phase obtained after the
alcoholysis reaction.
disadvantages
deactivation and/or lixiviation of the catalysts
usage, the increase in of the time reaction, higher molar ratio
of alcohol/fatty material.
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Technological scheme of biofuels production
(within RG project).
R1
MeOH
Rectifying
column
R2
H2O
CH4
Combustion,Q
Rapeseed
oil
Hydrogen
Glycerin
Green
Diesel
240
0

2,0 P
340
0

4,0 P
20% RO
30% BD
20% RO
80% BD
Peculiarities of processes:
- Conjugation of interesterification and hydrocracking processes
- Incomplete conversion of rapeseed oil (up to 80%)
- 50% biodiesel + 50% green diesel
Biodiesel
50% to consumer
Methanol
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Technological scheme of biofuels production
(within RG project) Interesterification.
R1
MeOH
Rectifying
column
R2
H2O
CH4
Combustion,Q
Rapeseed
oil
Hydrogen
Glycerin
Green
Diesel
240
0

2,0 P
340
0

4,0 P
20% RO
30% BD
20% RO
80% BD
HC
H
2
C
H
2
C O
O
O
R
1
O
R
2
O
R
3
O
+ CH
3
OH
H
+
OH
-

HC
H
2
C
H
2
C
OH
OH
OH
+ H
3
C
O
R
O
T=60
0
C
Peculiarities of process:
- Heterogeneous catalyst
- One step of interesterification
- Conditions: 240
0
, 2.0 P,
- trickle-bed reactor employment
Biodiesel
50% to consumer
Methanol
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Development of heterogeneous catalysts for plant
oils interesterification
Heterogeneous basic catalysts : MAl
12
O
19
(M = Ca, Sr, Ba),
so-called hexaaluminates
Cristal structure - magnetoplumbit and |-Al
2
O
3
Advantages of hexaaluminates
Chemical stability
Thermal stability
Possibility of catalysts regeneration
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Development of heterogeneous catalysts for plant oils
interesterification

rapeseed oil
, % Sr-La-O > Ba-La-O > Y-Mg-O La-Mg-O > Ba-Al-O
700
> Sr-Al-O
700

2240-2251cm-1
, mol/m
2
2.23 1.77 1.55 1.35 1.21 1.16
0 2 4 6 8 10
0
20
40
60
80
100
R
a
p
e
s
e
e
d

o
i
l

c
o
n
v
e
r
s
i
o
n
,

%
Reaction time, hours
Sr-Al-O (700)
Sr-Al-O (1200)
Ba-Al-O (700)
Ba-Al-O (1200)
Y-Mg-O (750)
La-Mg-O (750)
Sr-La-O (750)
Ba-La-O (750)
Concentration of middle base centers (determined via vibrational C-D
frequencies (v(CD)) of CDCl
3
adsorbed on samples) is correlated with activity of
catalysts
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Contents of the Presentation
I. Situation in World concerning renewable and local fuel
sources
II. The innovative catalytic ways of biomass processing for the
energetics within international projects and perspective
directions
II.I. Biofuels from wood
II.II. Improved technology of biodiesel production
II.III. Green diesel production
II.IV. Other perspective directions of biofuels production
III. Answer to a question: Can biomass replace fossil oil and
natural gas as feed stock for motor fuels production or not?
www.catalysis.ru
30
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Technological scheme of biofuels production
(within RG project). Hydrodeoxygenation
R1
MeOH
Rectifying
column
R2
H2O
CH4
Combustion,Q
Rapeseed
oil
Hydrogen
Glycerin
Green
Diesel
240
0

2,0 P
340
0

4,0 P
20% RO
30% BD
20% RO
80% BD
Biodiesel
50% to consumer
Methanol
H
3
C
O
R
O
H
2
Cat

Alkanes
Peculiarities of process:
- Heterogeneous catalyst
- One step of hydrocracking
- Conditions: 340
0
, 5.0 P,
- trickle-bed reactor employment
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Hydrodeoxygenation of biodiesel :
Structure of biodiesel:
Methyl ether of linolenic acid
(
19

33

2
) 8 %
Methyl ether of linoleic acid
(
19

35

2
) 20%
Methyl ether of oleic acid
(
19

37

2
) 59%
Methyl ether of erucic acid
(
23

45

2
) 3%
Methyl ether of stearic acid
(
19

39

2
) 10%
1 2
3
2
3
1
2
3
- Plant oil
- Biodiesel
- Green diesel
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Hydrodeoxygenation of biodiesel in the
presence of nickel catalysts
250 275 300 325 350 375 400
20
30
40
50
60
70
80
90
100

,
%
,
0
C
Ni-Cu/CeO
2
-ZrO
2
Ni-Cu/ ZrO
2
Ni-Cu/ CeO
2
Ni / ZrO
2
Ni/ CeO
2
CeO
2
-ZrO
2
250 300 350 400
0
4
8
12
16
20

Y

(
C
H
4
/
b
i
o
d
i
e
s
e
l
)
Temperature,
0
C
P =1,0
LHSV=2 h
-1
1. Ni-Cu/ZrO
2
-CeO
2
is the most active catalyst of hydrodeoxygenation of biodiesel
2. Process of the methanization begins at temperature 280
0
with nickel catalysts,
addition copper moves the beginning of the methanization in high temperature zone
Temperature
C
o
n
v
e
r
s
i
o
n

o
f

b
i
o
d
i
e
s
e
l
,

%
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Hydrocarbons
1. High-cetane diesel components production from biodiesel
Biodiesel
Mild
Hydrocracking
Bio-hydrogen
C
12
-C
17
diesel
Peculiarities:
Using of non-sulfided
and Ni-based catalysts
Process conditions:
290-340
o
C, 3,0-8,0 MPa H
2
Cetane value - 100
Application
Employment as
improved additive to
traditional diesel
O
O H
2
C
O
O
HC
O
O H
2
C
R
1
R
2
R
3
O
O H
3
C
R
Plant oils
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Products of fatty acids triglycerides hydrocracking at
the mild conditions (0,5 MPa H
2
)
Alkanes
C
7
-C
19
Carbonic acids
Aldehydes
Methyl esters of fatty acids
Alcohols
Ketones
Wax
products +
4
+
2
+
2
O C
O
R
O C
O
R
O C
O
R
R OH
R C
O
H
R C
O
CH
3
R C
O
R
R C
O
OR
R C
O
OCH
3
R C
O
OH
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Activity of Ni-Cu/CeO
2
-ZrO
2
at the severer conditions
(
2
=7,0 P =360
0
, LHSV= 1,1 h
-1
)
Y = mole
4
/ mole TGs C
15
- C
18
alkanes yields
0 2 4 6 8 10 12 14
0
5
10
15
20
Y
,
[
m
o
l
e
/
m
o
l
e
]
Time (h)
0 2 4 6 8 10 12 14
0
10
20
30
40
50
60
70
80
90
100
Y
i
e
l
d
s

o
f

C
1
5
-
C
1
8
,

m
o
l
.
%
Time (h)
0 4 8 12 16 20 24 28
0 4 8 12 16 20 24 28
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UIC
Possible scheme of non-food renewable feedstock
processing for biofuels production
Jatropha oil
Algae
Biodiesel
Green diesel
Transetherification
Mild hydrocracking
+ CH
3
OH
+ CH
3
OH
+ H
2
+ H
2
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37
UIC
The most perspective directions for transportation biofuels production
(for diesel engine )
Biomass
Wood
Solid
bio-waste
Bio-oil
Plant oil
Fats
Algae
Liquid
Bio-waste
Gasification
+
2
Shift
Bio-H
2
Mild
hydrocracking
Green Diesel
Oil
(problem: high content of sulfur)
Merits:
Renewable
Low content of sulfur
Possibility of fuels
production with different
composition
Transetherification
Biodiesel
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UIC
Yearly Energy TW yr Ej
Solar Energy to Earth 178000 5500000
Adsorbed by Atmosphere 120000
Adsorbed by Earth 53000 3700000
Adsorbed by Terrestrial 16000
Terrestrial Photosynthesis (<1%) 128 ~4000
Available for Biomass
Conversion
46 ~1426
Energy Demand Today 14 ~430
Energy Demand in 2050 >30 600-1800
Estimates Biomass in 2050 100-350
TW= Tatra Watts year/year Ej= Exa joules (=10
18
joules)
Supply of Biomass Today Versus the Total Global
Energy Requirement
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The conception of renewable energetics in the field
of development of fuel production processes
Concerning social aspect
Initial feedstock should be from non-food economics sector
Concerning provision aspect
Economic of biomass accretion is sufficient .
Concerning ecological aspect
Technology has to be power efficient and ecological
Concerning commercial aspect
Technologies have to be competitive (without development of new
technologies it is not possible)
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UIC
Thank you very much for
your attention !