recent developments in hydrothermal processing of algae · · 2016-11-0411 jim oyler with the...
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Recent Developments in Hydrothermal Processing of AlgaeDC ELLIOTTPacific Northwest National Laboratory
Bioenergy 2016, The National Algal Biofuels Technology Review, Washington, DC, July 14, 2016
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Outline
HTL at PNNL Upgrading of HTL biocrudeCHG of aqueous phasePreliminary TEA/LCACommercialization and future work
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Box Flow for Algae Application
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Simplified HTL Process Flow Diagram
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Solids Conc.[wt%]
Ash [wt%,dry basis]
Density[g/mL]
17-26 7-28 ~1.05
HTL Run ConditionsSteady state window duration: 2-3 hoursAverage temperature: 330-350°CAverage pressure: 2890-2925 psigSlurry feed rate: 1.5 L/h (LHSV=2-4 L/L/h)
AlgaeSlurry
(as processed)
AlgaeBiocrude
(as recovered)
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HTL Results from Algae Slurry
Biocrude Properties
Carbon [wt% dry] 79.4
Hydrogen [wt% dry] 10.1
H:C 1.51
Oxygen [wt% dry] 3.8
Nitrogen [wt% dry] 4.8
Sulfur [wt% dry] 1.4
HHV [mJ/kg] 39.2
TAN [mgKOH/goil] 54
Density [g/mL] 0.99
Viscosity [cSt, 40°C] 245
Moisture [wt%] 6.6
Ash [wt%] 0.40
Filterable Solids [wt%] 0.05
No
rmal
ized
Mas
s Yi
eld
No
rmal
ized
Car
bo
nYi
eld
Tetraselmis Marine Algae
Note: The solids concentration in the Tetraselmis was 17.8 wt% DAF.
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Mini-scale Fixed Bed Hydrotreater
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Reactor: ½” ID, ¾” OD, 25” long, 3/16” thermal wellHeater block: aluminum sheath (3” OD, 9” length) wrapped with heating tape; insulated.
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HT Product Compared to Biocrude from Algae
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HTL biocrude from algae can be upgraded to a hydrocarbon fuelGood HDN, HDO, and HDS achieved with conventional catalyst
Analyses Tetraselmis
Biocrude HT (95h)
Carbon [wt%] 79.4 87.0
Hydrogen [wt%] 10.1 14.9
H:C atomic ratio 1.5 2.1
Nitrogen [wt%] 4.8 <0.05
Oxygen* [wt%] 3.8 0.9
Sulfur [ppm] 14,000 15
Moisture [wt%] 6.6 <0.5
Density [g/cm3] 0.99‡ 0.78†
Viscosity [cSt] 245‡ 1.4†
TAN [mg KOH/g] 54 <0.01
*Oxygen by difference †At 20°C ‡At 40°C
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Analytical Data for Distillate Fractions
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Sample ID# Fraction C H N O TAN KF
61573-62-D1 naphtha 83.41 14.15 <0.05 0.80 <0.01 <0.5
61573-62-D2 jet 86.19 13.67 0.10 0.60 <0.01 <0.5
61573-62-D3 diesel 85.39 13.83 0.14 0.84 <0.01 <0.5
Sample ID# Fraction
Sulfur ASTM D5453 (ppm)
Flash Point
(micro-cup) °C
Cloud Pt ASTM D5773
(°C)
Pour Pt ASTM D5949
(°C)
Freezing Pt ASTM D5972
(°C) Cetane
61573-62-D1 naphtha 18.1
61573-62-D2 jet 12.6 49.5 -41.6 -48 -36.9
61573-62-D3 diesel 9.4 3.2 3 4.2 58.7
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• “Sister technology” to Hydrothermal Liquefaction (HTL)
• Can be used on any organic rich aqueous stream
• Produces methane gas rather than oil (catalytic action)
• Compact means to do “digestion” providing a fuel gas (CH4/CO2) without residual sludge
• Provides potential to recycle nutrients in biomass
Catalytic Hydrothermal Gasification
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Partner
Solix Algae HTL Oil HTL H2O CHG H2O
Samples of Materials
Description of CHG
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Preliminary Algae TEA – Potential Improvements & Preliminary LCA
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Increased yields, solids loading, and reactor space velocity are possible with further testing.Combined improvements could reduce fuel MFSP by about half.
0.0
10.0
20.0
30.0
40.0
50.0
12% Solids(BaseCase)
15% Solids 20% Solids no CHG
g C
O2
-e/M
J d
iese
l
Fuel Use
FuelDistribution
BiocrudeUpgrading
BiocrudeTransport
BiocrudeProduction
GHG Reductions: 54% 66% 74% 61%
Solids loading impacts GHGs (and $).Reduction from petroleum fuel is >50% for all cases.
$0.0
$0.5
$1.0
$1.5
$2.0
$2.5
$3.0
$3.5
$4.0
$4.5
$5.0
$5.5
Base case BiocrudeYield45%
HTL FeedSolids20%
HTLLHSV4hr-1
CombinedLarge/Small
WWTPs
HT Yield0.9 g/g drybiocrude
MFS
P, $
/gge
up
grad
ed f
uel
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Sensitivity Analysis – Saltwater Algae Case
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-$10.0 -$5.0 $0.0 $5.0 $10.0 $15.0
Hydrotreating Catalyst Life, years (5 : 2 : 1)Upgrading Capital (-40% : base : +40%)
CHG Catalyst Cost $/lb (30 : 60 : 120)CHG Catalyst Life, yrs (2 : 1 : 0.5)
Naphtha Value, $/gallon ($3.75 : $3.25 : $1.50)Project Contingency (0% : 10% : 20%)
CHG Capital Cost (-40% : base : +40%)HTL Capital (-40% : base : +40%)
Total Project Investment (-10% : base : +40%)Plant Scale Dry Feedstock, ton/d (2500: 1340 : 500)
No CHG - Recycle Untreated HTL AqueousInternal Rate of Return, IRR (0% : 10% : 20%)
Fuel Yield (+10% : base : -20%)Feedstock Cost, $/AFDW ton (430: 1100 : 2000)
Cost Change from Baseline Case – Saltwater Algae
TEA Cost Variability
Techno-Economic Analysis of Whole Algae Hydrothermal Liquefaction (HTL) and Upgrading System: Freshwater versus Saltwater AlgaeY Zhu, S B Jones, D B Anderson, R T Hallen, A J Schmidt, K O Albrecht, D C Elliott2015 Algae Biomass Summit, September 29 - October 2, 2015 Washington, DC
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Scale-Up and Technology Transfer
Genifuel is the PNNL licensee.Federal Laboratory Consortium Award for Excellence in Technology Transfer R&D100 Award Engineering challenges remaining include;
slurry pumping, efficient separations, heat integration
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Jim Oyler with the 1000 L/day (of 20 wt% BDAF) Hydrothermal Processing Pilot System continuous HTL/CHG system for algal feedstockNAABB-Reliance-PNNL-Genifuel
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Scale-Up and Technology Transfer
HPPS -- Made in AmericaTechnology developed at PNNLSystem design by GenifuelAssembled in ColoradoShipped to IndiaOn-site at RIL.
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Scale-Up and Technology Transfer
Being installed at the RIL algae processing site in Gagva, India
Expected start-up Q3 2016 Near Jamnagar
Largest petroleum refinery complex in the world
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