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8/4/2019 Design Catalytic Process for Biofuel Production
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www.catalysis.ru1 UIC
DESIGN OF CATALYTIC PROCESSES FOR
BIOFUELS PRODUCTION
III RUSNANOTECH 2010
Vadim A. Yakovlev
Valentin N. Parmon
Boreskov Institute of CatalysisNovosibirsk, Russia
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www.catalysis.ru2 UIC
Contents of the Presentation
I. Situation in World concerning renewable and local fuel
sources
II. The innovative catalytic ways of biomass processing for theenergetics within international projects and perspectivedirections
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 andnatural 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 andthe 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 andenergy:
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 biomass2. Lower technological level of biomass processing incomparison with oil refining
On the whole now the situation in bioenergetics issimilar 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 NewEnergy Finance (2010).Note: The final biofuel product from each pathway, and its associated conversion cost, has beencompared 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 theenergetics within international projects and perspectivedirections
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 andnatural gas as feed stock for motor fuels production or not?
8/4/2019 Design Catalytic Process for Biofuel Production
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Biomass
Pyrolysisplant
Biomass
Pyrolysisplant
Biomass
Pyrolysisplant
StandardRefinery
Upgrader
BiomassPyrolysis
plant
Transportation fuels
Chemicals
Heat and power
Schematic representation of the biomass-pyrolysis-upgrading-refinery concept
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Fractionationduring and
aftercondensation
Biomassresidues
Co-processing inconventional
petroleum refineryDe-oxygenation
Hydrocarbon-rich fraction
Lignin-richfraction
ConversionDerivatives of hemicellulosesand celluloses
Conventional fuelsand chemicals
Liquefaction
Note: hydrocarbon-rich fractions are formed when the biomass feedstock contains asignificant amount of extractive substances; e.g the case for forestry residues.
Energyproduction
Processresidues
Oxygenated products
(blending)
role of BIC
Netherlands BTG, University of Twente, Shell Global SolutionsInternational, University of Groningen, Albemarle Catalysts Co.Finland VTT, Helsinki University of Technology
France CNRS-IRC, ALMA Consulting Group, Metabolic ExplorerGermany - Ineos-Phenolics, UHDE, Institute of Wood Chemistry HamburgUnited Kingdom - Johnson MattheySweden - STFI-PACKFORSKSlovenia - Slovenian Institute of ChemistryRussia - Boreskov Institute of Catalysis
List of BIOCOUP project participants
Tasks of BIC within the projectDevelopment of bio-oil deoxygenation catalysts
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What is bio-oil?
Liquid (bio-oil)
Upgraded biocrudeoil
HDOH2
catalysts
up to 70 mass %
to dry biomass
Dry Biomass
Flash pyrolysisT > 450 0C, < 1 s,
heating rates > 1000 0C
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
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LMM Lignin:Catechols, ligninederived phenols andguaiacols ( 13%)
OH
R
OH
R
Acids (4%) CR
O
OHCR
O
OHC
O
HO
Aldehydes,Ketones, Alcohols
( 15%)
Sugars (34%)
HMM Lignin ( 2%)
dehydration ( H2O)
hydrogenolysis ( H2O)
decarbonylation ( CO)
decarboxylation ( CO2)
decarboxylation ( CO2)
cat
T
cat
T, H2
cat
T, CO
cat
T
cat
T
Upgrading of Bio--Crude--Oil via Catalytic Deoxygenation
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Hydrodeoxygenation catalysts developmentas key step of HDO process development
Traditional catalysts for
hydrodeoxygenation (HDO):
1. Sulfided Ni-Mo/Al2O3, Co-Mo/Al2O32. Pd, Pd-Pt, Rh-based catalysts
These catalysts dont fit
for bio-oil upgrading:- Noble catalysts are veryexpensive for large-scaleprocesses- Sulfided catalysts aredeactivated 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 $2250Pt $1703Pd $625Ru $178Ni $ 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
US$
/Troyonce
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
Al2O3, SiO2, C-SiO2
, Al2O3- SiO2, Cr2O3,
CeO2, ZrO2, CoSiO3
Step 1: Screening of HDO catalysts
Catalysts Rh/CoSiO3 Rh/ZrO2 Rh/ CeO2
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/Al2O3 Rh/SiO2 RhCo/SiO2
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: anisoleTemperature: 300oCPressure 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/Al2O3
(Albemarle)
IC3-47
(BIC)
Ni/ Cr2O3
(Chirchik)
Rh/CoSiO
(BIC)
H2pressure, MPa 0,5 0,5 0,5 0,5
Temperature, 0C 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 iC
iC
HDO degree corresponds to the selectivity of hydrogenated products formation:
- the concentration of oxygen-free iproduct
- the concentration of iproduct
Ni/ Cr2O3
Benzene hydrogenation into
cyclohexane
S/Ni-Mo/Al2O3
Oil hydrotreating
Step 2: Ni-based catalysts
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Catalysts screening and comparison with the commercial catalysts
Catalyst S/Ni-Mo/Al2O3
(Albemarle)IC-3-47(BIC)
Ni/ Cr2O3
(Chirchik)
Products
selectivity, %
cyclohexane 8,5 24,3 9,5benzene 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
desiredproduct
Step 2: Ni-based catalysts
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System NiCu/ Al2O3
Catalyst metal, % wt. supportCu Ni
24.5Cu 24,50 - Al2O35.92Ni18.2Cu 18,20 5,92 Al2O313.3Ni11.8Cu 11,80 13,30 Al2O313.8Ni6.83Cu 6,83 13,80 Al2O3
16Ni2Cu 2,00 16,00 Al2O320.8Ni -- 20,80 Al2O3
Catalyst conversion,% HDO, %
Quartz 2,8 0
Al2O3 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-1g-1
0,66
0,30
0,34
0,33
0,22
Step 3: Optimization of Ni-Cu catalysts composition
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In-situXRD analysis of NiCu/ Al2O3 system(under the hydrogen atmosphere, heating up to 300 )
Support(-Al2O3) 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 Ni1-xCux
Step 3: Optimization of Ni-Cu catalysts composition
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System NiCu/ Al2O3
TPR analysis(thermo-programmed reduction)
1. The presence of copper
promotes the nickel oxide
reduction at a lowertemperatures.
2. The addition of copper
into Ni/Al2O3 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 atHDO reaction conditions)
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www.catalysis.ru21 UIC48M General Assembly 38
RUG-Results Highlight
Exploratory Catalyst Screening
Pyrolysis oil, 350 oC, 200 bar H2, 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
Pin
e oil
Ru/C 5
wt%
Ru/C
3.33wt
%
Ru/C
2wt%+a
ctPd
/C
PdPt
/SiO
2-Al
2O3 (
Albe
)
Rh/C
eO2
Rh/Z
rO2
Rh/Co
SiO
3
Rh/Z
rO2
RhPd/
ZrO
2
RhPt/
ZrO
2
Pd/Z
rO2
PdPt/
ZrO
2
Pt/Z
rO2
NiCu/A
l2O3
FeCu/A
l2O3
NiCu/
ZrO
2
NiCu
/CeO
2(co
)
NiCu
/CeO2
(wet)
NiCu
/C
NiCu
/CeO2-
ZrO
2
crac
king
(NiC
u/d-Al
2O3)
crac
k+Ni
Cu/C
eO2-Zr
O2
NiCu
/sib
unite
NiCu/C
eO2
Catalyst
Oxygenconte
nt(wt-%)
noble metals
cheaper transition metals
: flowable products at RT
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www.catalysis.ru22 UIC
Contents of the Presentation
I. Situation in World concerning renewable and local fuel
sources
II. The innovative catalytic ways of biomass processing for theenergetics within international projects and perspectivedirections
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 andnatural gas as feed stock for motor fuels production or not?
1 I d T h l f Bi di l P d ti
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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
H2SO4 orNaOH
Traditional technology:
Manufacture of biodiesel:more than 12 million tons in 2009
Prediction:biodiesel production growth ~10-15% per year
O
OH2C
O
O
HC O
OH2C
R1
R2
R3
CH3OH OHH2C
OHHC
OHH2C
O
OH3CR
Wh h l ?
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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 cost2 - 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 thealcoholysis reaction.
disadvantages deactivation and/or lixiviation of the catalysts usage, the increase in of the time reaction, higher molar ratio
of alcohol/fatty material.
Technological scheme of biofuels production
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Technological scheme of biofuels production(within RG project).
R1
MeOH
Rectifyingcolumn
R2
H2O
CH4
Combustion,Q
Rapeseedoil
HydrogenGlycerin
GreenDiesel
2400
2,0 P
34004,0 P
20% RO30% BD20% 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
Biodiesel50% to consumer
Methanol
Technological scheme of biofuels production
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Technological scheme of biofuels production(within RG project) Interesterification.
R1
MeOH
Rectifyingcolumn
R2
H2O
CH4
Combustion,Q
Rapeseedoil
HydrogenGlycerin
GreenDiesel
2400
2,0 P
34004,0 P
20% RO30% BD20% RO
80% BD
HC
H2C
H2C O
O
O
R1
O
R2
O
R3
O
+ CH3OH
H+
OH-
HC
H2C
H2C
OH
OH
OH
+ H3C
O
R
OT=60
0C
Peculiarities of process:
- Heterogeneous catalyst- One step of interesterification- Conditions: 2400, 2.0 P,- trickle-bed reactor employment
Biodiesel50% to consumer
Methanol
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Development of heterogeneous catalysts for plant
oils interesterification
Heterogeneous basic catalysts : MAl12O19 (M = Ca, Sr, Ba),
so-called hexaaluminates
Cristal structure - magnetoplumbit and -Al2O3
Advantages of hexaaluminates
Chemical stability
Thermal stability
Possibility of catalysts regeneration
Development of heterogeneous catalysts for plant oils
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Development of heterogeneous catalysts for plant oilsinteresterification
rapeseed oil, % Sr-La-O > Ba-La-O > Y-Mg-O La-Mg-O > Ba-Al-O700 > Sr-Al-O700
2240-2251cm-1, mol/m2 2.23 1.77 1.55 1.35 1.21 1.16
0 2 4 6 8 100
20
40
60
80
100
Rap
eseedoilconversion,
%
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-Dfrequencies ((CD)) of CDCl3 adsorbed on samples) is correlated with activity ofcatalysts
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www.catalysis.ru29 UIC
Contents of the Presentation
I. Situation in World concerning renewable and local fuelsources
II. The innovative catalytic ways of biomass processing for theenergetics within international projects and perspectivedirections
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 andnatural gas as feed stock for motor fuels production or not?
Technological scheme of biofuels production
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Technological scheme of biofuels production(within RG project). Hydrodeoxygenation
R1
MeOH
Rectifyingcolumn
R2
H2O
CH4
Combustion,Q
Rapeseedoil
HydrogenGlycerin
GreenDiesel
2400
2,0 P
34004,0 P
20% RO30% BD20% RO
80% BD
Biodiesel50% to consumer
Methanol
H3CO
R
O
H2
CatAlkanesPeculiarities of process:
- Heterogeneous catalyst- One step of hydrocracking- Conditions: 3400, 5.0 P,- trickle-bed reactor employment
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Hydrodeoxygenation of biodiesel :Structure of biodiesel:
Methyl ether of linolenic acid
(19332) 8 %
Methyl ether of linoleic acid(19352) 20%
Methyl ether of oleic acid(19372) 59%
Methyl ether of erucic acid(23452) 3%
Methyl ether of stearic acid(19392) 10%
1 2 3
2
3
1
2
3
- Plant oil
- Biodiesel
- Green diesel
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Hydrodeoxygenation of biodiesel in thepresence of nickel catalysts
250 275 300 325 350 375 400
20
30
40
50
60
70
80
90
100
,%
,0C
Ni-Cu/CeO2-ZrO
Ni-Cu/ ZrO2
Ni-Cu/ CeO2
Ni / ZrO2
Ni/ CeO2
CeO2-ZrO
2
250 300 350 400
0
4
8
12
16
20
Y
(CH4/biodiesel)
Temperature,
0
C
P =1,0
LHSV=2 h-1
1. Ni-Cu/ZrO2-CeO2 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
Conversionofbiodiesel,%
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Hydrocarbons
1. High-cetane diesel components production from biodiesel
Biodiesel
Mild
Hydrocracking
Bio-hydrogen
C12-C17
diesel
Peculiarities:Using of non-sulfidedand Ni-based catalysts
Process conditions:290-340oC, 3,0-8,0 MPa H2
Cetane value - 100
ApplicationEmployment asimproved additive totraditional diesel
O
OH2C
O
O
HC O
OH2C
R1
R2
R3
O
OH3CR
Plant oils
Products of fatty acids triglycerides hydrocracking at
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Products of fatty acids triglycerides hydrocracking atthe mild conditions (0,5 MPa H2)
Alkanes C7-C19
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 CO
H
R CO
CH3
R CO
R
R CO
OR
R CO
OCH3
R CO
OH
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Activity of Ni-Cu/CeO2-ZrO2 at the severer conditions(2=7,0 P =360
0, LHSV= 1,1 h-1 )
Y = mole 4/ mole TGs C15- C18 alkanes yields
0 2 4 6 8 10 12 140
5
10
15
20
Y,[mole/mole]
Time (h)
0 2 4 6 8 10 12 140
10
20
30
40
50
6070
80
90
100
Yield
sofC15-C18,m
ol.%
Time (h)
0 4 8 12 16 20 24 28 0 4 8 12 16 20 24 28
Possible scheme of non-food renewable feedstock
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Possible scheme of non food renewable feedstockprocessing for biofuels production
Jatrophaoil
Algae
Biodiesel
Green diesel
Transetherification
Mild hydrocracking
+ CH3OH
+ CH3OH
+ H2
+ H2
The most perspective directions for transportation biofuels production
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The most perspective directions for transportation biofuels production(for diesel engine )
Biomass
Wood
Solidbio-waste
Bio-oil
Plant oil
Fats
Algae
LiquidBio-waste
Gasification
+ 2
Shift
Bio-H2
Mildhydrocracking
Green Diesel
Oil (problem: high content of sulfur)
Merits:
Renewable Low content of sulfur Possibility of fuels
production with differentcomposition
Transetherification
Biodiesel
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Thank you very much for
your attention !