of Renewable
Feedstocks
JOHN HOLLADAY
Energy and Environment Directorate
john.holladay@pnnl.gov
CAAFI R&D SOAP-Jet webinar series
November 14, 2014
November 14, 2014
Overview
Fuel characteristics
Refinery overview
Modeling assessments
National Advanced Biofuels Consortium
(NABC)
Opportunities
Technology advancements
FCC (co-processing VGO with bio-oil)
Hydrotreating (bio-oil and biocrude)
Alkylation (alcohol to jet)
Fuel characteristics
Desired Characteristics
Miscible with petroleum-based fuels and transportable in current pipelines
Meet performance & storability criteria designed for jet engines
it must be jet fuel
Optimize desired hydrocarbon chain/boiling point for aviation (mid-distillates)
Lower cost
Reduce H2 demand and pressure
Improve product quality
cycloparaffins
n-paraffins
(C8-C16)
aromatics
iso-paraffins
Aromatics in jet fuel also helps elastomers in the fuel system to swell and seal properly at
low temperature
Iso-paraffins and n-paraffins are good (Btu content) / Aromatics are bad above certain
amount (minimum needed to ensure seal swell)
November 14, 2014
Refineries
Capital cost
Unit operations within the refinery
Insertion points
Capital costs
Plant size and economies of scale
Cellulosic
Biorefinery
<5,000 bpd
$77,000
285,000/bpd
(US DOE)
Corn Ethanol
5,000 -10,000 bpd
US Petroleum Refinery
Fischer-Tropsch (CTL)
up to 550,000 bpd
US 8,000 bpd
China 30,000+ bpd
South Africa 160,000 bpd
$16,000
34,000/bpd
(USDA)
http://www.usda.gov/oce/rep
orts/energy/EthanolSugarFeasi
bilityReport3.pdf
Refinery conversions:
$0 140,000/bpd
(CERA)
http://www.ihs.com/pdfs/ihscera-upgrading-refining-mar2013.pdf
Refining
Complex but efficient
~100 years experience
~750 refineries
~85M BBL of crude refined
daily
~50M BBL transport fuels;
~6M BBL of aviation fuel
(~250 M gallons/day; 90 B
gallons/year)
Scientific/technical Challenge
Catalysts developed for
the petrochemical and
refining industries are
generally not stable to
bioprocessing
Engineering (materials of
construction, etc)
9
10
Insertion point 1
11
Insertion point 3
Biomass products blended into near
finished fuel
Biomass is converted to a
near-finished fuel or
blendstock
Blended component must
meet all applicable
standards (ASTM) for
finished fuel
Allows tailoring processes
to unique properties of
biomass
Allows blending to be
controlled by refiner
Strict rules on blending
outside of the refinery may
require re-testing of
controlled properties
12
Insertion point 2
Biomass Intermediate is fed into
facilities within the refinery
Conversion processes
Hydrocrackers
Fluid catalytic crackers
(FCC)
Cokers
Finishing processes
Hydrotreating
Naphtha HT
Distillate HT
etc
Specialty units
Isomerizing
Reforming
Alkylating
13
Conversion Processes
Decreases molecule sizes to convert heavier materials into
distillation ranges of transportation fuels
Conversion units are also capable of removing some level
of contaminants
Feed boiling
Range (oF)
C:H increase
mode
Cracking
mode
Coker
C rejection as
coke
Thermal
Vacuum
resid
1050+
FCC
C rejection as
coke
Fluid
catalyst
Vacuum gas
oil
610-1050
Hydrocracker
H addition using
metal cat
Fixed bed
catalyst
Vacuum gas
oil
450-1050
Unit
Feedstock
14
Hydrotreaters
Remove heteroatoms (such as S, N, O) via catalytic reaction with H2
Allow finished products to meet spec or to protect sensitive units
Naphtha
90-380F
Kerosene/Diesel
380-610F
610-1050F
Temperature
Pressure
LHSV
15
Specialty Units
Isomerizing
Converts n-paraffins to isomers (higher octane or alkylation feed)
Fixed bed of metal/acid catalyst at lower temp than reforming
Alkylating
Converts isobutane & isobutylene to isooctane
HF or H2S acid catalyst (containment!!), sensitive to feed carbon number
Reforming
Upgrades octane of naphthas by generation of aromatics (+ H2) from
napthenes (+ paraffins)
Fixed bed of chlorided Pt/Al2O3 catalyst particles at low pressure & high temp,
sensitive to S, N in the feed
16
Technical Focus
High level assessment of impact of
incorporation of bio-derived intermediates
in U.S. petroleum refineries
Surveys availability of biomass near
petroleum refineries in the 2022 timeframe
Preliminary considerations of biointermediate compatibility with petroleum
intermediates
Offers a refiners perspective
Public document
Data Sources
KDF for biomass resources
EIA for refinery resources
Publically available biointermediate data
http://www.pnl.gov/main/publications/external/technical_reports/PNNL-22432.pdf
November 14, 2014
17
18
Refinery locations
Bio-oil production in
2022*
A: Initial look
suggests
refineries &
biomass may
fit
19
Refiners perspective
safety, reliability, predictability, profitability
Risk
Type of Bio-oil Intermediate
Lowest Well defined, consistent quality,
such as single molecules (e.g.,
ethanol, butanol, farnesene)
Insertion
Blending
units
Refinery Challenges
Blending, product performance and distribution
of products that include the bio-component
Evaluating and managing potential stability,
toxicity and environmental issues
Preliminary Conclusions
Focus on Gulf Coast
Biomass availability, river logistics
Primary supply is imported crude (priced off Brent)
Limited access to Bakken, Marcellus/Utica, Canadian supplies
21
November 14, 2014
Technology development
FCC
Hydrotreating/hydrocracking
Alkylation
22
23
Scale
Scale
Feed Preheater
Feed Pump
Stabilizer Column
Feed
Tank
Control
Valve Meter
Condenser
Feed
Tank
Stripper
Feed
Storage
Tank
#2
Heat Exchanger
Feed
Storage
Tank
#1
Riser Reactor
Control
Valve
Regenerator
Meter
Dispersant Steam
Stripping Steam
26 licensed DCR pilot units have been constructed throughout the world
25
November 14, 2014
100% VGO
9.3
0.02
2.1
6.7
12.4
53.1
90.2
79.5
15.4
4.9
5.2
0.0
0.0
10.3
0.0
Conditions
Rx exit temp = 970F
Catalyst temp = 1300F
Feed temp = 250F
Pressure = 25 psig
O
O
O
O
O
Vegetable oil is
chemically as close to
petroleum as any
biomass feedstock
Not favored
technology for jet
fuel from veg. oils
26
temperature profile
O
O
27
23.0
39.5
7.5
53.0
55.5
6.5
38.0
28
50.0
14
49.5
13
49.0
12
48.5
11
48.0
10
LCO (430-700F) wt%
47.5
Coke wt%
7.2
13.50
6.9
13.25
13.00
6.6
12.75
6.3
12.50
82.0
82.5
83.0
83.5
84.0
82.0
82.5
Conversion wt%
83.0
83.5
84.0
Adding raw pyrolysis oil results in more coke, less gasoline and less LCO
29
Degree of Catalytic
Hydrotreating
(O content, dry
basis)
Percentage
pyrolysis oil
co-processed
Yield Observations
while coprocessing
None
(38 wt% O)
~200F (93C)
up to 5 wt% with
difficulty
Increased coke,
reduced gasoline
Mild
(22wt% O)
~200F (93C)
up to 3 wt% with
difficulty
Increased coke,
reduced gasoline
Medium
(11% O)
Up to 700F (370C)
10 wt%
Severe
(2% O)
Up to 700F (370C)
10 wt%
Note: typical FCC feed pre heat temperatures are 300 to 700F (150-370C)
Pyrolysis oil levels >10 wt% were not tested since refineries are unlikely to run above these levels
31
Ian Barnett, Issue 36 PyNe Newsletter, IEA Bioenergy Task 34 (Dec 2014)
32
Hydrotreating
Hydrotreating
Work done at PNNL
Current studies are on
hydrotreating neat bio-oil
Fast pyrolysis bio-oil
Bio-oil is not miscible with
petroleum
Severe catalyst challenges
Hydrothermal Liquefaction
biocrude
Moves further into middistillate/distillate range
More miscible with
petroleum
Easier to process
34
Petroleum hydrocracking
Pyrolysis
oil
HTL
biocrude
Naptha
HDS
Kerosene
HDS
ATM
resid HDS
Gas oil
HDS
Mild HCK
Single
STG HCK
Resid
HCK
HDO
HDO
45
555
460
422
358
1150
660
~3400
~1800
35
Workhorse equipment
40 cc dual T zone
packed bed reactor
400/800 cc dual T
zone packed bed
36
plug
FP oil density: 1.2 g/cc
Catalysts: RuS/C
CoMoS/C
T: 250 - 410C
P: 15 MPa H2
Space velocity: 0.1-0.2
Start-up after each plugging event required replacement of
about 10% of the catalyst bed
November 14, 2014
H2 demand = 5 - 8 g
H2/100 g oil (dry basis)
37
percent distilled
60
50
batch 1
44.2%
40
42.4%
batch 2
30
jet
20
naphtha
10
0
0
50
100
150
200
250
temperature, degrees Celsius (corrected to 1 atm)
300
350
Jet fuel mid-distillate may provide the aromatic/cyclic portion of jet fuel
Jet A1
Spec
-47
39
0.775
Starting
SPK
-63
42
0.753
cycloparaffins
n-paraffins
Products
Feedstock
HDCJ
(Kior)
Forest residues
aromatics
iso-paraffins
CH
(UOP)
Agriculture residues
Fast pyrolysis
Hydrothermal liquefaction
feedstock
operating temperature
environment
catalyst
operating pressure
residence time
carbon yield to bio-oil
Dry Biomass
450-500C
inert gas
none
1 atm
< 1 sec
70%
Wet biomass
350C
aqueous condense phase
alkali reagent often used
200 bar
5 to 30 min
50% (typical for lignocellulosics)
Pyrolysis bio-oil
HTL Biocrude
6,900 Btu/lb
14,200 Btu/lb
oxygen content
water content
viscosity@40C
thermal stability
40%
25%
low (50 cSt)
no
15%
5%
high (4,000 cSt)
yes
cSt = centistokes
42
43
Basis: 100 g
Pine forest residue
Solids
3g
bio-crude
35 g (61% of C)
Gas
1g
Hydrocarbon
Product 30 g
(60% of C)
Separation
Hydrotreator
138 bar
HTL
Reactor
350C
200 bar
H2
1g
Gas
10 g
Separation
Feed
Prep
-200
Filter
Purge: 52 g (27% of C)
(available for CHG which
produces a medium Btu gas)
Aqueous
5g
Step
Carbon Efficiency
61%
Hydrotreating yield
96%
Combined
59%
44
Parameter
Unit
Value
Mass Balance
Carbon Balance
Oil Yield
Carbon Yield
Gas Yield
Produced Water
Yield
H2 consumption
%
%
g dry/g dry feed
g C/g C in feed
g gas/g dry feed
g produced water
per g dry feed
g H2/100g dry feed
101
99.8
0.85
0.96
0.034
Parameter
Unit
bio-crude
Upgraded
H/C ratio
dry basis
1.14
1.36
Oxygen
Wt% dry
14
0.009
Nitrogen
ppm
3800
520
Sulfur
ppm
650
19
Oil density
g/ml
1.13
0.912
Moisture
Wt%
13
0.35
TAN
mg KOH/g
140*
0.76
0.16
3.3
45
Hydrothermal liquefaction
is suitable for a broad range of wet feedstocks
Algae Paste
Wood Paste
Hydrotreated
Algae HTL Oil
Hydrotreated
Wood HTL Oil
46
Low lipid
high lipid
105-400
0.20
85
2.6-3.8
Mass balance
91-98%
0.8 0.94
84-85%
Hydrogen, Wt%
13.5%
Oxygen, Wt%
1.2-1.8%
Nitrogen, Wt%
0.08-0.25%
Sulfur, Wt%
<0.005%
HT Product
High paraffin HTL Products
Fractionated Product
Diesel Fuel
48
Moving forward
Alkylating
Alkylating
Today will focus on
production of jet fuel from
ethanol feedstock
Also used as a means to
improve quality of fast
pyrolysis bio-oils at PNNL
Using alkylating technology
from refinery to make high
quality fuels
50
Steel, PVC,
Ferroalloys
Associated
Gas,
Biogas
Solid Waste
Industrial,
MSW, DSW
Reforming
CO
CO + H2
Inorganic CO2
Biomass
Gasification
Renewable H2
CO2 + H2
CO + H2 + CO2
Gas Fermentation
Source: LanzaTech
Fuels
Chemicals
Renew
able
CO2 + H2Electri
O + ecity
51
LanzaTech Technology
Gas
Fermentation
Reception
Recovery
Alcohol
Catalytic
Product
Conversion
Diesel
Jet
Gasoline
Separation
Alcohol to jet
OH
catalyst
catalyst
heat
Can make
isoparaffins or
cyclics dependent
on reaction
conditions
Dimer (C8)
1. H2 catalyst
2. Distillation
Trimer (C12)
Tetramer (C16)
C4butanol, i-butanol
Cobalt, Gevo , et al
fuel primarily C12 and
C16 (limited mol. chains)
C2ethanol
Swedish Biofuels (+CO/H2)
PNNL/ Imperium (SPK)
broad chain length
Gas
fermentation
Catalytic
upgrading
fractionation
ATJ summary
Jet A, JP-8
cycloparaffins
Product
Feedstock
ATJ-SKA
(Swedish)
Butanol /ethanol
n-paraffins
aromatics
iso-paraffins
cellulosic ethanol
ATJ-SPK
Hydrocarbon mix
depends on the technology
butanol-produces C8,12 and16
Ethanol give range of hydrocarbons
Source: Dr. Timothy Edwards, Air Force Research Laboratory
gas fermentation
Conclusions
In the last 2 years we have made tremendous strides
addressing challenges in refinery integration
FCC operations
Are possible with certain bio-oils co-processed with
refinery intermediatesproduce gasoline-rich streams
Hydrotreating operations
Are required for upgrading bio-oils and also used with
biocrudes
Pyrolysis/liquefaction lead to cyclic hydrocarbons
from wood (unless ring opening is deployed)
Hydrogen demand varies by technology, and is
significantly reduced with HTL
Alklyating operations
Alcohol to jet moves us out of the classical liquefaction
paradigm
56
Next steps
57
Back up material
58
59
Oxygen (Dry)
Nitrogen
Sulfur
Moisture
Density, g/ml
Viscosity, cSt, 40C
Oil TAN mgKOH/g
Pine
Corn
Stover
12%
0.29%
0.01%
9%
1.11
3100
55
17%
1.1%
0.04%
8%
1.10
3400
44
60
Low lipid
High lipid
2.2
2.2
Temperature, C
350
348
Mass Balance
102%
97%
91%
96%
65%
64%
81%
Bio-Oil Composition, Dry Weight Basis
82%
77.0%
77.6%
Hydrogen, Wt%
10.4%
10.6%
Oxygen, Wt%
8.0%
7.2%
Nitrogen, Wt%
4.2%
4.0%
Sulfur, Wt%
0.3%
0.3%
61