NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.
Refinery Integration of Bio-oil
Robert M. Baldwin
Principal Scientist
Presentation to California Air
Resources Board
December 13, 2016
Innovation for Our Energy Future
Innovation for Our Energy Future
Overview
1) Background and basics
2) Previous studies: NABC
a) Goals
b) Outcomes
3) Proposed new study, DOE/BETO
Innovation for Our Energy Future
Pyrolysis
Bio-Crude
Fuels
and
Chemicals Biomass
Co-Processing Bio-oil with Crude Oil
Integration with Existing Refining Infrastructure
Refining
Infrastructure
The Basic Idea is Simple
Crude Oil
Typical petroleum refinery ≥ 500,000 BPD Biorefinery @ 2,000 TPD => ~7,400 BPD bio-crude
Innovation for Our Energy Future
Biomass Pyrolysis Oil (Bio-oil) Characteristics
Challenging Characteristics of Pyrolysis Oil (from wood)
• Insoluble in hydrocarbons
• Moisture content 15 - 30 wt %
• pH ≈ 2.5; TAN >100
• Elemental composition, wt %
- C: 54 - 58
- H: 5.5 - 7.0
- O: 35 - 40
• HHV: 16 - 19 MJ/kg
• Distillation residue: up to 50wt %
• Phase Separation & Instability
- a lighter, water soluble, carbohydrate-rich fraction
- a more dense, viscous, oligomeric lignin fraction
- ‘ages’ with time; viscosity increase
Innovation for Our Energy Future
Why Do This?
1) Introducing bio-oil into the refinery provides ready
pathway for introducing renewable carbon into
transportation fuels industry (low-hanging fruit)
2) Utilize multi-trillion-dollar infrastructure already in place
a) Petroleum refineries
b) Transportation and distribution systems
3) High impact outcomes
a) RINs for refiners
b) Implementation likely: LCFS in CA (coming soon elsewhere!)
Innovation for Our Energy Future
NABC
The National Advanced Biofuels Consortium (NABC) is a collaboration among U.S. Department of Energy national laboratories, universities, and private industry that is developing technologies to produce infrastructure-compatible, biomass-based hydrocarbon fuels.
The consortium, led by the National Renewable Energy Laboratory and Pacific Northwest National Laboratory, is funded by the U.S. Department of Energy under the American Recovery and Reinvestment Act and by NABC partners.
Three years, $45MM
Innovation for Our Energy Future
NABC Goals
The goal of the NABC is to accelerate
development of technologies for sustainable,
cost-competitive, drop-in fungible
hydrocarbon fuels from lignocellulosic biomass
– investigate technologies from both thermochemical
and biochemical platforms
– Determine feasible blending points in the refinery
– Couple technical work with rigorous TEA and LCA
• Focus on cost-effective and sustainable technologies
Innovation for Our Energy Future
NABC Refinery Integration
Biomass
Existing Refinery Infrastructure
Atm
os
ph
eri
c &
Va
cu
um
Dis
tilla
tio
n
Gas
L Naphtha
H Naphtha
LGO
VGO
Atm Resid
Vac Resid
Reform
FCC
Alky / Poly
HT/HC
Coker
Gasoline
Jet FuelDiesel Fuel
Crude Oil
Refinery-Ready Intermediates
Finished Fuels & Blendstocks
Conversion Process Upgrading Process
Insertion Point #1
Insertion Point #2
Insertion Point #3
Innovation for Our Energy Future
NABC Outcomes
Innovation for Our Energy Future
Petroleum Refinery Overview
Source: Chevron Motor Gasolines Technical Review http://www.chevronwithtechron.com/products/documents/69083_MotorGas_Tech_Review.pdf
Crude Unit (Straight-Run or Virgin Intermediates)
Coker
Fluid Catalytic Cracker
10
Hydrocracker
Reformer
Innovation for Our Energy Future
-
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
150 200 250 300 350 400 450 500 550 600 650 700
AP
I Gra
vit
y
Volume Average True Boiling Point (Deg F)
NABC Gasoline Streams NABC Diesel Streams
Finished Gasoline Blend Finished Diesel Blend
Gasoline Blend Component Diesel Blending Components
LSR
LCN
Alky
Ref
MCN
Naphthas (C5 – 400 °F)
Refinery Integration – Naphthas
11
Hydrothermal liquefaction (HTL): Possibly directly blended based on bulk properties but mild hydroprocessing may be required to blend appreciable volumes in gasoline pool.
Possible Insertion Point(s): Mild Naphtha Hydroprocessing or Blending
Hydropyrolysis (HYP): Highly aromatic material possesses significantly lower hydrogen to carbon ratio relative to typical refinery cracked naphthas (coker and FCC). The material would likely join heavy cracked naphtha refinery streams for hydroprocessing.
Possible Insertion Point(s): Cracked Naphtha Hydroprocessing
Catalysis of lignocellulosic sugars (CLS): Possibly directly blended based on bulk properties but mild hydroprocessing may be required to blend appreciable volumes in gasoline pool.
Possible Insertion Point(s): Mild Naphtha Hydroprocessing or Blending
Innovation for Our Energy Future
-
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
150 200 250 300 350 400 450 500 550 600 650 700
AP
I Gra
vit
y
Volume Average True Boiling Point (Deg F)
NABC Gasoline Streams NABC Diesel Streams
Finished Gasoline Blend Finished Diesel Blend
Gasoline Blend Component Diesel Blending Components
Refinery Integration – Distillates
12
Hydrothermal liquefaction (HTL): Resembles the properties of FCC light cycle oil (LCO) and would likely follow the same processing path.
Possible Insertion Point(s): Hydroprocessing or Hydrocracking
Catalysis of lignocellulosic sugars (CLS): Resembles the properties of FCC light cycle oil (LCO) and would likely follow the same processing path.
Possible Insertion Point(s): Hydroprocessing or Hydrocracking
HT SR Kero
HC Kero
HT CD HT SRD HC Dist
Distillates (400 – 700 °F)
Fermentation of lignocellulosic sugars (FLS): Highly paraffinic material likely to possess desirable diesel blending properties.
Possible Insertion Point(s): Diesel Blending
Hydropyrolysis (HYP): Likely to be more highly aromatic than FCC light cycle oil (LCO), which suggests significant hydrogen addition would improve potential for diesel blending.
Possible Insertion Point(s): High-Pressure Hydroprocessing or Hydrocracking
Innovation for Our Energy Future
(5)
-
5
10
15
20
25
30
35
40
45
50
55
60
65
150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1,000 1,050 1,100 1,150 1,200
AP
I Gra
vit
y
Volume Average True Boiling Point (Deg F)
Virgin Intermediates Coker Intermediates FCC Intermediates
NABC Gasoline Streams NABC Diesel Streams NABC Heavies Streams
Finished Fuel Blends
13
Refinery Integration – Heavies
Hydrothermal liquefaction (HTL): Possesses similar bulk properties to coker gas oil.
Possible Insertion Point(s): Resid FCC or Hydrocracker
Hydropyrolysis (HYP): Properties resemble FCC heavy cycle oil (CHO) or unconverted bottoms (slurry oil).
Possible Insertion Point(s): Hydrocracker, Coker, Asphalt or Bunker Fuel Blending
Catalysis of lignocellulosic sugars (CLS): Resembles a high boiling point residual material such as vacuum tower bottoms.
Possible Insertion Point(s): Resid FCC, Coker or Asphalt / Lubes
Resids (1000+ °F)
Gas Oils (700 – 1000 °F)
Innovation for Our Energy Future
NABC Blending Model
Conventional 87 Gasoline
Conventional 93 Gasoline
On-Road Diesel (15 wppm S)
Marine Diesel (500 wppm S)
Heating Oil (2,000 wppm S)
Refinery Blendstocks (ACTUAL data from approximately 10 U.S. refineries)
NABC Whole Oils (Upgraded for refinery insertion if applicable)
NABC Whole Oil FRACTIONATION
Bunker Fuel Oil (Heavies)
SELL BLEND
Refinery Naphthas
Refinery Distillates
Product Specs
NABC Naphthas
NABC Distillates
NABC Heavies
Pricing Data
PIMS (Process Industry Modeling System) by
Upgrading (Hydroprocessing, Fluid Cat Cracking,
Coking)
BUY
14
Refinery Residuals
Innovation for Our Energy Future
Key Remaining Questions and Issues
1) Distillability of bio-oil a) Functional relationship between oxygen content and bio-oil
volatility (AKA distillability)
2) Impact of feedstock type and liquefaction technology
3) Key properties for refiners a) Stability
b) Miscibility
c) Corrosion
d) Fouling (heat exchangers)
e) Carbon deposition
f) Catalyst poisons
g) Distribution and speciation of organic oxygenates in fuel-range products
4) Imperative to de-risk utilization of bio-oil as a refinery feedstock
a) Similar to what the refining community encountered when switching from light sweet crude to heavy sour crude
Innovation for Our Energy Future 16 National Renewable Energy Laboratory Innovation for Our Energy
Hydrotreater
Gas H2
Areas of corrosion and heat exchanger
fouling concern
Equipment Integrity Issues
Innovation for Our Energy Future 17 National Renewable Energy Laboratory Innovation for Our Energy
Hydrotreater
Gas H2
•Severity required to ensure low/no oxygen in product? •Bio-oil Impact on catalyst activity, life, yields, product quality •incremental H2 needed
Hydrotreating Issues
Innovation for Our Energy Future
Hydrotreating Severity in the Refinery
0
2
4
6
8
0 400 800 1200 1600 2000 2400
Liq
uid
Ho
url
y Sp
ace
Vel
oci
ty
Pressure, psig
Naphtha Temp = 570-700 oF
Light Distillate Temp = 625-700oF
Heavy Distillate Temp = 645-750oF
Vacuum Gas Oil Temp = 680-750oF
Bio-oil Temp = 660-800oF
Innovation for Our Energy Future 19 National Renewable Energy Laboratory Inovation for Our Energy
Hydrotreater
Gas H2
Impact of surviving oxygen molecules on catalyst performance,
yields, product quality?
Is this step needed?
•Can dilute blends of bio-oil be cat cracked? YES •Properties of oxygenates in products?
Is FCC favored over H/C?
Is there any Resid? If So, Coking study
needed
Examples: Conversion/Upgrading Process Issues
Innovation for Our Energy Future
New DOE/BETO Project
Goal: identify optimal strategies with high carbon efficiency, low CAPEX & OPEX
• Multiple liquefaction technologies to be examined • Impact of partial upgrading to be assessed • Multiple refinery ‘insertion points’ will be
evaluated • Experimental work coupled with rigorous TEA, LCA,
and refinery modeling • Work on biogenic C tracking (LANL) and corrosion
and fouling (ORNL)
Innovation for Our Energy Future
Project Strategy
Innovation for Our Energy Future
Thank You – Questions?
Innovation for Our Energy Future
Back-up Slides
Innovation for Our Energy Future
• Processing bio-oil in the FCC
• Petrobras/NREL study (pilot scale system)
• Up to 20% raw bio-oil in petroleum-derived Gas Oil
• No loss in gasoline yield up to 10% bio-oil
• Product distribution essentially unchanged
• 2% renewable carbon in liquid products (14C NMR)
• At 20% bio-oil some yield loss observed
• 3 – 5% renewable carbon in liquid products
• High content of phenolics in cracked products
• Carbon in bio-oil converted to carbon in liquids ~ 30%
• Engine testing on gasoline and diesel showed no problems
• Other studies (BIOCOUP) indicate importance of upgrading
prior to co-processing
NREL/ENSYN/Petrobras Project
Innovation for Our Energy Future
Integration in the FCC
FCC Butenes & Butanes
FCC Gasoline
FCC Light Cycle Oil
In-Plant VGOCrude Oil
Gasoline
Blendstock
ULS Diesel
Blendstock
Biomass
Heavier CrudeProducts
AlkylationGasoline
Blendstock
Gasoline Hydrotreating
Diesel Hydrotreating
Fluid Catalytic Cracking
(FCC)
Crude Oil Fractionation
Scope for Process Modeling, TEA and LCA Through Finished Fuel Blendstocks
LighterCrudeProducts
Pyrolysis
Purchased VGO
Pyrolysis Oil
Heavy FCC Products (HCO, Slurry Oil)
Light FCC Products (Fuel Gas, Propane, Propylene)
Innovation for Our Energy Future
What About the Economics?
Innovation for Our Energy Future
But With Crude at $50/BBL
Innovation for Our Energy Future
Infrastructure Compatibility
Distillation
Gasoline, Diesel, Jet
Fuel, Bunker C, etc. Naphtha, LGO,
VGO, etc.
Crude Oil
Existing Refinery Infrastructure
LC Biomass Intermediates Finished Products and
Blendstocks Research
Areas Research
Areas
Existing Transmission, Storage & Distribution
Infrastructure
Existing Vehicle Infrastructure
Fuel Synthesis
Innovation for Our Energy Future
(5)
-
5
10
15
20
25
30
35
40
45
50
55
60
65
150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1,000 1,050 1,100 1,150 1,200
AP
I Gra
vit
y
Volume Average True Boiling Point (Deg F)
Virgin Intermediates Coker Intermediates FCC Intermediates
NABC Gasoline Streams NABC Diesel Streams NABC Heavies Streams
Intermediate / Product Comparison
Resids (1000+ °F)
Gas Oils (700 – 1000 °F)
Distillates (400 – 700 °F)
Naphthas (C5 – 400 °F)
HTL
CLS
HYP
HYP
CLS
HTL
NABC Naphthas
NABC Distillates NABC Heavies
CLS
HTL
HYP
FLS
29
FLS Fermentation of Lignocellulosic Sugars
CLS Catalysis of Lignocellulosic Sugars
HTL Hydrothermal Liquefaction
HYP Hydropyrolysis
Innovation for Our Energy Future
(5)
-
5
10
15
20
25
30
35
40
45
50
55
60
65
150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1,000 1,050 1,100 1,150 1,200
AP
I Gra
vit
y
Volume Average True Boiling Point (Deg F)
Virgin Intermediates Coker Intermediates FCC Intermediates
NABC Gasoline Streams NABC Diesel Streams NABC Heavies Streams
Finished Fuel Blends
Intermediate / Product Comparison
CLS
HTL
HYP
NABC Heavies
Gasoline
Diesel
30
Kero / Jet
HTL
CLS
HYP
NABC Naphthas
HYP
CLS
HTL
NABC Distillates
FLS FLS Fermentation of Lignocellulosic Sugars
CLS Catalysis of Lignocellulosic Sugars
HTL Hydrothermal Liquefaction
HYP Hydropyrolysis
Innovation for Our Energy Future
-
5
10
15
20
25
30
35
40
45
50
55
60
65
70
75
80
85
150 200 250 300 350 400 450 500 550 600 650 700
AP
I Gra
vit
y
Volume Average True Boiling Point (Deg F)
NABC Gasoline Streams NABC Diesel Streams
Finished Gasoline Blend Finished Diesel Blend
Gasoline Blend Component Diesel Blending Components
Naphthas & Distillates (Hysys Results)
HTL
CLS
HYP
HYP
CLS
HTL
LSR
LCN
Alky
Ref
MCN
HT SR Kero
HC Kero
HT CD HT SRD HC Dist
Distillates (400 – 700 °F)
Naphthas (C5 – 400 °F)
FLS
31
FLS Fermentation of Lignocellulosic Sugars
CLS Catalysis of Lignocellulosic Sugars
HTL Hydrothermal Liquefaction
HYP Hydropyrolysis
Innovation for Our Energy Future
Reality for Refinery Integration