Innovation for Our Energy Future Refinery Integration of ... · Asphalt or Bunker Fuel Blending...

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


Overview

1) Background and basics

2) Previous studies: NABC

a) Goals

b) Outcomes

3) Proposed new study, DOE/BETO


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


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


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!)


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

http://www.eere.energy.gov/

http://www.recovery.gov/

http://www.anl.gov/index.html

http://www.lanl.gov/


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


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


NABC Outcomes


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

http://www.chevronwithtechron.com/products/documents/69083_MotorGas_Tech_Review.pdf


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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


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Refinery Integration – Distillates

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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


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Virgin Intermediates Coker Intermediates FCC Intermediates

NABC Gasoline Streams NABC Diesel Streams NABC Heavies Streams

Finished Fuel Blends

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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)


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


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


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


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)


Project Strategy


Thank You – Questions?


Back-up Slides


• 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


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)


What About the Economics?


But With Crude at $50/BBL


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

http://www.google.com/imgres?imgurl=http://media.canada.com/b2fd399c-8611-4580-92ea-44f66ab1b1a2/sun0805n-gas 5.jpg&imgrefurl=http://www.canada.com/vancouversun/features/hosedatthepumps/index.html&h=375&w=375&sz=66&tbnid=v7a4GDGoGRUuEM:&tbnh=122&tbnw=122&prev=/images?q=gas+pump+photo&hl=en&usg=__F-73UzrozfC8dYzUiju3rDLZM9Y=&ei=vLBcSufHIY22M5bQsK4C&sa=X&oi=image_result&resnum=3&ct=image

http://images.google.com/imgres?imgurl=http://www.planebuzz.com/Boeing787_high.jpg&imgrefurl=http://www.planebuzz.com/planemakers/&h=1753&w=2300&sz=1754&tbnid=XMhKYh1zH_EXKM:&tbnh=114&tbnw=150&prev=/images?q=picture+boeing+787&um=1&start=3&sa=X&oi=images&ct=image&cd=3

http://www.google.com/imgres?imgurl=http://leblog.exuberance.com/images/Honda-Civic-Mobil-gas-station.jpg&imgrefurl=http://leblog.exuberance.com/finance_economy/&usg=__CtCbVY3AcYljb4HFYt8LxTA8kCE=&h=375&w=530&sz=78&hl=en&start=1&sig2=glygVwLN3uo12hpxa3H5XQ&tbnid=e0vuhrhCxX7p8M:&tbnh=93&tbnw=132&prev=/images?q=chevron+gas+station+photo&hl=en&sa=G&ei=E7NcSq28K4PQlAf0yuTaDA


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Intermediate / Product Comparison

Resids (1000+ °F)

Gas Oils (700 – 1000 °F)



HTL

CLS

HYP

HYP

CLS

HTL

NABC Naphthas

NABC Distillates NABC Heavies

CLS

HTL

HYP

FLS

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FLS Fermentation of Lignocellulosic Sugars

CLS Catalysis of Lignocellulosic Sugars

HTL Hydrothermal Liquefaction

HYP Hydropyrolysis


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Finished Fuel Blends

Intermediate / Product Comparison

CLS

HTL

HYP

NABC Heavies

Gasoline

Diesel

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Kero / Jet

HTL

CLS

HYP

NABC Naphthas

HYP

CLS

HTL

NABC Distillates

FLS FLS Fermentation of Lignocellulosic Sugars



HYP Hydropyrolysis


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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



FLS

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FLS Fermentation of Lignocellulosic Sugars



HYP Hydropyrolysis


Reality for Refinery Integration

Innovation for Our Energy Future Refinery Integration of ... · Asphalt or Bunker Fuel Blending...

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