Recent Progress in Biocrude Upgrading

and Co-processing

David C. Dayton, Ph. D.

RTI Senior Fellow and Biofuels Director

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 Bio-crude Upgrading Overview
Investigate the impact of bio-crude quality in the hydroprocessing step
• Steady-state deoxygenation activity, hydrogen demand, and process severity with bio-crude of
various quality (wt%O and chemical composition)
• Long-term operation to determine upgrading catalyst stability and lifetime (500-1000 hrs)
• Refinery integration and co-processing strategies

Hydrogen
Simplified RTI HDT Unit Process Flow Diagram To Gas Outlet
Wet Test
Gas Feed Meter

Condensate
Compressor
Hydrogen

Product Gas/Vapors

Pot
Hydrogen
Product Gas/Vapors

Low Pressure
Biocrude

Separator
Oil product

High Pressure

Nitrogen Stripper
Separator
Biocrude
HT Reactor 1

HT Reactor 2

Feed Tank

Oil/Water
Separator
Reactor Effluent

Biocrude Sampling
Scale

Liquid Product
Pot
Feed Pump

Liquid Product
Biocrude Aqueous
Feed Tank Bypass Product
Storage
Biocrude Nitrogen
Scale
Feed Pump

Reactor volume: 350 mL LHSV - 0.1 to 1.0 Max. design pressure - 3000 psig
Catalyst volume: 20 - 250 mL Flow rates - 50 to 250 mL/h Max. design temperature - 450 C
 Bio-crude Upgrading Overview
Catalyst Loading, Sulfidation, and HDT Process Conditions
• HDT Catalyst: HaldorTopsøe Bio-Cat
• Catalyst Sulfidation: In-situ with H2S in H2 balance.
• Bio-crude flow rate: 50-250 ml/h
• Mass Balance Protocol: Allow at least 48 hours of run time prior to performing
mass balance.
• Experiments continue until pressure drop across reactor > 60-100 psig or feed
runs out

Typical Test
Parameters
Conditions
Temperature 290 – 350 °C
Pressure 1450-2000 psig
LHSV 0.125 - 0.5 1/h
H2/oil 2000-3300 Nl/l

Analysis of Bio-crude and HDT products include:

Elemental Analysis(CHNSO), GC-MS, FTIR, NMR, Carbon Number Distribution, Distillation by
ASTM D1160, SG 60/60 by ASTM D4052, Kinematic Viscosity by D445, and Karl Fischer Titration.
Bio-crude Upgrading Overview
Challenges:
 High process severity (T, P, LHSV) is required for bio-crude upgrading
 Bio-crude upgrading is limited by catalyst deactivation
 Poor bio-crude thermal stability (reactivity) causes reactor
fouling/plugging. 100
Fraction A
90
Fraction B
80 Fraction C
Fraction D
70
Fraction E

60 Fraction F
Fraction G
Weight %

50 Fraction H
Fraction I
40
Fraction J
30
Residual
20 Losses

10

0
0 100 200 300 400 500 600 700 800
Temperature (°C)

Bio-crude quality beyond wt% O.

How does bio-crude chemical composition impact upgrading?
Strategies for Bio-oil/Bio-crude Upgrading
Strategy Process
Pre-processing • Ultrafiltration
• Ion exchange
• Chemical modification (esterification, etherification,
neutralization)
Stabilization • Mild hydrotreating
• 200°C, 1500 psig, Ru/C

Fractionation • Separations (Liquid-Liquid Extraction)

• Distillation (Thermal Stability)

Pyrolysis process • Catalysts, process conditions, and feedstocks to

control chemical composition. Target: ~15 wt% oxygen

Co-processing • Hydrotreat blends of petroleum refining intermediates

and bio-crude (5-50 vol%) to control oxygen and sulfur
content
Pine CFP Bio-crude Compositions
wt.% dry basis A B C D* E
C 72.7 73.1 69.7 76.6 63.7
H 7.1 7.1 7.2 7.9 6.7
N 0.6 0.3 0.3 0.5 0.5
O 19.6 19.5 22.8 15.0 29.6
H/C 1.17 1.17 1.24 1.24 1.26
100%
Unknown
90%
Anhydrosugars
80%
Multifunctional
GC-MS Peak Area

70% phenols
Monofunctional
60% phenols
PAH
50%
Mono-aromatic
40%
Acids
30%
Furanics
20%
Multifunctional
carbonyls
10%
Monofunctional
carbonyls
0%
Aliphatic
Feed A Feed B Feed C Feed D Feed E
 Pine Bio-crude Hydrotreating: Feedstock and Process Conditions

1.00
Pine Bio-crudes 365 hours TOS

0.98

0.96

0.94
Density, kg/L

0.92

0.90

0.88

0.86

0.84

0.82
Open Circles = no ΔP
0.80
0 50 100 150 200 250
Time on Stream, hours
Feed A, 0.5/h, 1450 psig, T1=290C, T2=350C Feed B, 0.25/h, 2000 psig, T=300C
Feed A, 0.5/h, 1450 pisg, T=350C Feed B, 0.25/h, 2000 psig, T=290C
Feed C, 0.125/h, 2000 psig, T1=280C, T2=350C Feed D, 0.25/h, 2000 psig, T=300C
Feed E, 0.35/h, 2000 psig, T=290C Feed E, 0.35/h, 2000 psig, T=300C
 Pine Bio-crude Hydrotreated Products
Feed B, 0.25/h, 2000 psig, T=300C Feed E, 0.35/h, 2000 psig, T=290C
100 100
90 90
GC-MS Peak Area %

80 80

GC/MS Peak Area %

70 70
60 60
50 50
40 40
30 30
20
20
10
10
0
0
12 20 28 36 44 52 60 68 76 84 92 100 108 116 132 146 191 219 218 242 263 338 12 28 36 50 60
Time on stream (TOS), h Time on Stream (TOS), h

Unknown
Feed D, 0.25/h, 2000 psig, T=300C
p Oxygenates
100
Methoxy-Phenolics
GC-MS Peak Area %

90
80
70 Simple Phenols
60
50 OxyAromatics
40
PAH
30
20 Di-Aromatic
10
0 Mono-Aromatics
24 32 40 48 56 60 64 68 72 76 84 92 96 116
Time on stream (TOS), h Olefins

Naphthenes

Paraffins
 Bio-crude Separations
Solvent Extraction Distillation
Overhead
INPUT Mass (kg) INPUT Mass (kg)
Solvent soluble
(solvent)
Bio-crude 26.1 Extract 31.4

Distillation Column
(Extract) Recovered
Biocrude Solvent Solvent 29.3
Tank Scale
Scale OUTPUT Mass (kg) OUTPUT Mass (kg)
Mixer-Settler

Raffinate 22.6 Solvent 24.3

Solvent
Tank Extract 32.6 Bottoms 6.3
Scale
Distillate
100
Bottoms Unknowns
Solvent Insoluble 90
(Raffinate) Raffinate Bottoms Aliphatic hydrocarbons
Tank Tank 2.72
Scale Scale
80
9.83 Mono-functional
70 4.26 26.89 phenols
GC-MS Peak Area %
31.24 Furanic compounds
• Solvent extraction 60
22.05
Mono-functional
separates out acids and 50 12.01
carbonyls
Multi-functional
anhydrosugars 40 8.75
carbonyls
30 Anhydrosugars
• Although not detected with 20
44.75
49.33
Acids
35.08
GC-MS, oligomers likely 10
Aromatic hydrocarbons
end up in the raffinate 0
(Mono-, Di-, Poly-)
Multifunctional
Biocrude Solvent Raffinate
phenolics
Extract
 Solvent Extracted Bio-crude Hydrotreating: Physico-chemical Properties
0.93

0.92

0.91 310C
320C
0.90
Density, kg/L

0.89
300C
0.88

0.87 Catalyst TK-341

0.86
H2 Flow Rate (sccm) 400
0.85
Feed Rate (g/h) 70-77
0.84

0.83 Pressure (psig) 2000

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time on Stream, hours Average Temperature (oC) 300
C H O diff LHSV (h-1) 0.35
0.3 1.5 2.3 1.8 2.2 2.2
100% 2.8 4.1 3.4 4.0 3.9 3.5
4.7 4.5 5.3 5.5
H2/oil ratio (Nl/l) 3300
90%
20.5
80%
70%
60%
50%
40%
30%
20%
10%
0%
0 13 21 27 39 48 56 64 72 80 90 96 100 108 120 132 144
Time on stream, hours
 Hydrotreated Product Compositions
Feed 300 °C 310 °C 320 °C
Unknown
100
Olefins
90
0.7
0.2 3.6 3.7 Oxygenates
80 2.0 4.6
GC-MS Peak Area %

3.5 12.0 7.9

70 23.2 15.2
18.0
14.2 8.9 17.2 19.4 Oxy-Aromatics
14.1
60 30.3 Multifuntional
34.3
29.2
33.6 29.9 Phenolics
50
28.4 32.0 29.6 Simple Phenols
31.6 30.2 30.2
40 30.1 29.1 29.0
27.5 PAH
30 3.4
49.1 Di-Aromatics
20 36.7
32.4 30.7
21.8 26.5 23.4 24.8 26.7 26.3 Mono-Aromatics
10 20.9 19.1 21.4 21.9 20.1 19.1
16.7
0.9
0 Paraffins
0 13 21 27 39 48 56 64 72 80 90 96 100 108 120 132 144
Time-on-Stream (TOS), hours Naphthenes
RCFP Bio-crude Production and Upgrading
12-L RCFP bio-crude produced in 2”FBR over 10 months
Average Hydrogen Consumption: 2.3 wt% Biomass

Reaction Conditions RCFP Bio-crude Composition

Catalyst: Mo/Al2O3 (GC-MS Area%) Elemental
Hydrogen: 80 vol%
Properties
Temperature: 460° C
Moisture, wt% 8.5
C wt%, dry 73.2
Carbon Mass H wt%, dry 7.3
Balance* Balance N wt%, dry 0.2
Aqueous 2.5 27.4 O (by diff) 19.3

Organic (C4+) 43.0 19.6

Liquid Bio-crude 26.4 15.9

C4-C6 16.6 3.7
Gas 26.8 13.1
Char+Coke 30.1 35.9
Total 102.4 96.0
 RCFP Bio-crude Upgrading: Physico-chemical Properties
0.96

0.95

0.94

0.93

0.92

0.91
Density, kg/L

0.90
Catalyst TK-341
0.89

0.88 H2 Flow Rate (sccm) 3300

0.87

0.86
Feed Rate (g/h) 62
0.85 Pressure (psig) 2000
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time on Stream, hours Average Temperature (oC) 300
C H O diff
100% 1.4 1.0 2.8 2.8 4.8 4.3 4.3 4.7 5.0 5.1 5.6 5.6 5.5
LHSV (h-1) 0.31
90% 19.3

80%
H2/oil ratio (Nl/l) 3300
70%

60%

50%

40%

30%

20%

10%

0%
0 13 25 37 49 61 73 85 97 101 113 125 137 144
Time on stream, hours
 RCFP Bio-crude Upgrading: Hydrotreated Product Compositions
Feed Products
100
Unknown
0.0 0.4
90 1.9 5.6 Olefins
6.0 9.1 11.8
80 16.0 22.1
17.5 19.1 20.7 Oxygenates
GC-MS Peak Area %

16.2
70 34.0
Oxy-Aromatics
23.6 47.0
60 Multifuntional
40.8 Phenolics
50 41.1 Simple Phenols
38.4
40 36.6 PAH
33.1
30 30.7 Di-Aromatics
24.9 25.7 26.1
48.3 24.3
23.2 Mono-Aromatics
20 35.6
27.9 24.9
10 22.3 Paraffins
18.2 15.4 13.4 12.1 11.2
7.6 9.8 8.4 8.1
0.0 Naphthenes
0
0 13 25 37 49 61 73 85 97 101 113 125 137 144
Time-on-Stream (TOS), hours
 Co-processing Bio-crude with Refinery Intermediates
30/70 30/70 30/70 30/70 30/70
30% Light Cycle Oil Property
LC1/LG LC2/LG CPO1/LG CPO2/LG CPO3/LG
(LC) or Partially H, wt % 12.46 12.14 12.80 12.58 12.31
Upgraded Bio-crude O, wt % - - 1.26 1.84 2.47
S, wt % 1.19 1.00 0.828 0.903 0.717
(CPO) blended with N, ppm 213 433 258 327 377
70% straight run diesel SG 0.863 0.873 0.861 0.867 0.882

LG LG+LC LG+CPO1 LG+LC2 LG+CPO2 LG+CPO3

0.85

• No additional pressure drop 0.84

with CPO
• 6% lower diesel yield from
CPO ([O] in feedstock and 0.83
SG 60/60

light and a heavy fractions

outside diesel range) 0.82
H2 pressure: 70 barg
• Lower H2 consumption for LHSV: 0.4 h-1
CPO compared to the LCO 0.81 H2/oil ratio: 625 NL/L
(HDS vs. HDO) Temperature: 330 - 345°C

0.80
0 500 1000 1500 2000
Run Hour (h)
 RCFP Bio-crude Co-processing with Light GasOil
Analysis Unit LG RCFP 10/90 RCFP/LG 15/85 RCFP/LG 20/80 RCFP/LG
SG at 60/60°F 0.8541 1.005 0.8667 0.8726 0.8782
O wt % - 9.65 - - -
S wt % 1.30 0.001 1.14 1.04 1.01
N wt ppm 148 425 165 180 201
H wt % 13.09 8.28 12.59 12.43 12.18
0.8500
10% RCFP 90%LG LG 20% RCFP 80% LG 15% RCFP 75% LG

0.8450
Pressure 50 – 70 barg 50 barg
(Inlet pH2) (725-1015 psig)
0.8400
SG 60/60
Temperature 340 – 360°C
40% loss relative
LSHV 2 h-1 activity for HDS
0.8350
H2/oil ratio 500 Nl/l

0.8300

H2 consumption (NL/L): 69 vs. 115-134

0.8250
0 200 400 600 800 1000 1200
Run Hour (h)
• > 1000 hours without shut-downs or severe deactivation
• Blended feed oxygen in the range 0.9 – 1.9 %wt
• Product oxygen ≤6 ppmw
• Approximately 89 % of RCFP bio-crude converted to hydrocarbons on weight basis
 Summary
1.00

0.98

0.96

0.94
Density, kg/L

0.92

0.90

0.88

0.86

Feed B, 0.25/h, 2000 psig, T=300C

0.84
Feed D, 0.25/h, 2000 psig, T=300C
Feed E, 0.35/h, 2000 psig, T=290C
0.82
RCFP Bio-crude, 0.31/h, 2000 psig, T=300C
SE Bio-crude, 0.35/h, 2000 psig, T=300C
0.80
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
Time on Stream, hours
Conclusions
Commercially-relevant steady-state hydrotreating
• More anyhdrosugars and acids = faster reactor plugging
• Pyrolysis processes for minimizing thermally unstable
components
• Separations for removing undesirable components
• Co-processing (50% lower pressure) to minimize impacts of bio-
crude composition

Hydrotreating catalyst deactivation

• Mechanism
• Sulfur loss
• Recovery by increasing temperature

Total oxygen content for hydrogen demand

Oxygen speciation for upgrading process performance

Caution: What is not identified with GC/MS that causes additional

problems?
Acknowledgements

RTI Biomass Team Haldor Topsøe A/S

• Dr. Ofei Mante • Jostein Gabrielsen
• Dr. Phil Cross • Nadia Luciw Ammitzboll
• Joseph Weiner • Sylvain Verdier
• Jonathan Peters • Christian Ejersbo Strebel
• Gary Howe
• Kelly Amato
RTI Bio-crude Production Capabilities

Pilot-scale (1TPD) in situ Catalytic Fast Pyrolysis

• Continuous feed circulating fluidized bed
reactor/regenerator
• Pyrolysis temperature: 350-500 ºC
• Regenerator Temperature: 560-640 ºC
• Residence time: 0.5-1.0 s
• Biomass Feed Rate: 35-70 kg/h
• Bio-crude production rate: 20-50 gal/hr

Laboratory Fluidized Bed Reactor

System
• 2.5’’ fluidized bed reactor with 4’’ disengagement zone
• Biomass feeding rate: 2-5 g/min
• Liquid collection: 3 condensers and 1 ESP
• Non-condensable gases analyzed by micro GC
• Liquid product analyzed by Karl Fischer titration,
elemental analysis, GC/MS