Ctlti Hd i fBiCatalytic Hydroprocessing of Biomass Fast ... · Fast Pyrolysis Bio-oil to Produce Hydrocarbon ProductsHydrocarbon Products ... Fast pyrolysis Bio-oil Wet ----- Dry

C t l ti H d i f BiCatalytic Hydroprocessing of Biomass Fast Pyrolysis Bio-oil to Produce Hydrocarbon ProductsHydrocarbon Products

Presented at the International Conference on Thermochemical Biomass Conversion Science,

September 18, 2009

DC Elliott, TR Hart, GG Neuenschwander, LJ Rotness, AH Zacher

Outline

Introduction to biomass fast pyrolysis and upgrading to py y pg gpetroleum refinery feedstock

Results of catalytic hydroprocessing biomass fastResults of catalytic hydroprocessing biomass fast pyrolysis bio-oil

Biomass to End Use

BiofuelsFeedstock Feedstock

Biofuels– rail, truck,

pipelines– blenders

VehiclesCONVERSIONDISTRIBUTION END USE

Feedstock Production

Feedstock Logistics

Bioproducts

– blenders– fuel pumps

Bioproducts– rail, truck

Chemicals, Materials

Demonstration & DeploymentBiopower

Biopower– transmission

linesGrid

Integrated Biorefineries

Feedstock Production

Processing RD&DInfrastructure

Biochemical Conversion

Thermochemical Conversion

and Infrastructure

Impact of Biomass Liquefaction

Bio-oils have received interest as an alternative source of fuel.

CO2 neutralLow fraction of bonded sulfur and nitrogen

UsesUsesBoilers, kilns, turbinesMust be upgraded for use as a regular fuel

Removal of oxygenProperty improvement

Thermochemical Direct Liquefaction of Biomassof BiomassHydrothermal Liquefaction

~350ºC, 200 atm,350 C, 200 atm, biomass slurry in water, minutesReducing gas (maybe)Catalyst (maybe)Catalyst (maybe)

AlkaliMetals

Fast Pyrolysis500°C, 1 atm, dry, finely divided, < 1 secondInert atmospherepNon-catalytic

Comparison of Wood-Derived Bio-oils and Petroleum Fuel

Characteristic Hydrothermal Bio-oil Wet ---------- Dry

Fast pyrolysis Bio-oil Wet --------- Dry

Heavy Petroleum Fuely y

Water content, wt% 3-5 15-25 0.1Insoluble solids, % 1 0.5-0.8 0.01%Carbon, % 72.6-74.8 76.5-77.5 39.5 55.8 85.2Hydrogen, % 8.0 7.8 7.5 6.1 11.1Oxygen, % 16.3-16.6 12.5-14.1 52.6 37.9 1.0Nitrogen, % <0.1 <0.1 <0.1 0.3Sulfur, % <0.05 <0.05 <0.05 2.3Ash 0.3-0.5 0.3-0.5 0.2-0.3 <0.1HHV, MJ/kg 30 17 40Density g/ml 1 10 1 23 0 94Density, g/ml 1.10 1.23 0.94Viscosity, cp 3,000-17,000@ 60ºC 10-150@50ºC 180@50ºC

Unwanted Characteristics of Bio-oilcharacteristic problem solution

Low pH corrosion Adequate MaterialsNeutralizationHydroprocessing

High viscosity Handling Add waterPumping Add solvent

HydroprocessingInstability and Storage Avoid contact with hot surfacesInstability and temperature sensitivity

StoragePhase separationDecomposition and Gum formation

Avoid contact with hot surfacesStabilization or Refining through Catalytic Treatment

Add Water or DiluentsViscosity increase

Add Water or Diluents

Unwanted Characteristics of Bio-oil, cont.characteristic problem solution

Char and solids Combustion problems Liquid filtrationChar and solids content

Combustion problems Liquid filtrationEquipment blockage Hot gas filtrationErosion

Alk li t l D iti f lid i Bi t t tAlkali metals Deposition of solids in boilers, engines, and turbines

Biomass pretreatmentHot gas filtrationCatalytic upgrading

Water content Complex effect on heating value, viscosity, pH, homogeneity and other characteristics

Problem recognitionOptimization and control of water content according to applicationapplication

What Kind and Degree of Upgrading?

First, determine final use …Fuel for boilersFuel for boilersFuel for turbinesFuel for internal combustion enginesRecovery of chemicalsRecovery of chemicals

Determine upgrading requirement …Physical upgrading

Solvent additionSeparations

Chemical/catalytic upgradingy pg g

Bio-oil Upgrading to Liquid Fuels

Extrapolations from petroleum processing

Catalytic Cracking – 26% yieldC7 5H7O6 → 4C + 0.6C6H11 77.5 7 6 6 11.7

Catalytic Hydrotreatment – 49% yieldC7.5H7O6 + 7H2 → 5H2O + 0.5CO2 + C7H11

Comparison of Upgrading Processes

Catalytic Cracking• Atmospheric pressureAtmospheric pressure• No H2 required• Coking of catalyst may be a problem• Produces mostly aromatic hydrocarbons• Produces mostly aromatic hydrocarbons

Catalytic Hydrotreatmenty y• High pressure• Requires H2

• Produces aliphatic and aromatic hydrocarbonsProduces aliphatic and aromatic hydrocarbons

Hydrotreating of Biomass Pyrolysis Oilslight products

h d l dH2gasb d t

fast di

hydrogen recycle and byproduct gas reforming

2byproduct

fastpyrolyzer medium

products

char

HT

HC heavy

charbyproduct

biomass

aqueousbyproduct

aqueousbyproduct

HC yproducts

biomass

Pacific Northwest National Laboratory ContributionsContributions

Chemical and physical analysis of wood and peat fast p y y pand slow pyrolysis oil

2 stage hydrotreating of pyrolysis oil for gasoline2-stage hydrotreating of pyrolysis oil for gasolineElliott, D. C. and E. G. Baker. "Process For Upgrading Biomass Pyrolyzates." U.S. Patent Number 4,795,841, issued January 3, 1989Baker, E. G., and D. C. Elliott. "Method of Upgrading Oils Containing Hydroxyaromatic Hydrocarbon Compounds to Highly Aromatic Gasoline." U.S. Patent Number 5,180,868, issued January 19, 1993

N i th l h d t ti f di f l iNon-isothermal hydrotreating for upgrading of pyrolysis oil to stable fuels

Catalyst Development for Biomass ApplicationsApplications

Stable catalysts in the presence of watery p

Improved hydrogenation catalysts

Understanding the effects of biomass trace components on catalystsy

Catalytic Hydrogenation Development at Pacific Northwest National LaboratoryPacific Northwest National Laboratory

Early Work Present Work yBased on petroleum processing technologySulfided catalysts

Optimized for bio-oil productsNon-sulfided catalystsy

Exhaustive hydrogenationLiquid hydrocarbon fuel products

yDirected hydrogenationLiquid fuel and chemical products

Highly aromatic productHigh hydrogen consumption

Mixed hydrocarbon products Targeted hydrogen consumption

Batch Reactor TestingImproved catalysts for bio-oil

hydrogenationrutheniumrutheniumpalladium

Small batch testing of model compoundscompounds

acetic acidguaiacol (2-methoxyphenol)furfural

Elliott, D.C.; Hart, T.R. “Catalytic Hydroprocessing of Chemical Models for Bio-oil.” Energy & Fuels, 23, 631-637, 2009. web publication, December 12, 2008.

Elliott, D.C.; Hart, T.R.; Hu, J.; Neuenschwander, G.G. “Palladium Catalyzed Hydrogenation of Bio-Oils and Organic Compounds.” U.S. Patent #7,425,657, 9/16/2008. p

Bench-Scale Continuous-Flow Catalytic Hydrogenation SystemHydrogenation System

•150 -- 450°C

• 0 1 -- 1 5 LHSV0.1 1.5 LHSV

• 75 -- 150 atm

• 1-10 m3 H2/L bio-oil

Current Research Activities

Continuous-flow bench-scale reactor tests have been performed to test catalysts and processing conditions.

99 hydrotreater data sets49 hydrocracking data setsy g

Recovered products are analyzed at PNNL andanalyzed at PNNL and UOP to determine composition and value

Elemental Analysis of Bio-oil Feedstocks

biomass carbon hydrogen oxygen nitrogen sulfur

mixed wood 44.53+/-2.7 7.24+/-0.4 46.05+/-1.5 0.16+/-0.01 0.028

mixed wood,heavy phase

56.08 6.90 39.60 0.46 NA

corn stover, 31.22 8.17 57.77 0.87 0.046,light phasecorn stover,heavy phase

52.74+/-2.8 7.07+/-0.6 37.33+/-6 1.12+/-0.2 0.16+/-0.01

whole corn stover

32.09 8.10 55.43 0.66 0.062

oak 42.50 7.16 49.74 0.12 0.008

poplar 46.35 7.00 41.61 0.05 0.007

Composition of Hydrotreated Bio-oils

bio-oil source H/C (dry)

C H O N S moisture

mixed wood 1.43 75.5 9.4 12.3 0.6 0.02 2.7 t li ht h 1 28 76 2 8 5 15 5 2 4 NA 2 6corn stover light phase 1.28 76.2 8.5 15.5 2.4 NA 2.6

corn stover heavy phase 1.40 76.2 9.4 12.7 2.0 0.06 3.5 whole corn stover 1.53 77.1 10.2 11.9 2.3 NA 2.9 oak 1.35 74.2 9.0 14.5 0.1 0.01 5.7

l (h t filt d) 1 33 73 1 8 6 17 9 0 2 0 16 3 5poplar (hot-filtered) 1.33 73.1 8.6 17.9 0.2 0.16 3.5

340°C, 2000 psig, 0.25 LHSV340 C, 2000 psig, 0.25 LHSV

Hydrocracking Product Oil Chemical Components Determined by GC MS/FIDComponents Determined by GC-MS/FIDComponent Groups O1 O2 O3 O4 Feed 1unsaturated ketones 0.00% 0.00% 0.00% 0.00% 0.00% carbonyls (hydroxyketones) 0 00% 0 00% 0 00% 0 00% 0 00%carbonyls (hydroxyketones) 0.00% 0.00% 0.00% 0.00% 0.00%naphthenes 70.77% 67.88% 69.67% 71.63% 4.22% phenol and alkyl phenols 0.00% 0.00% 0.00% 0.00% 15.68% alcohols & diols 0.00% 0.00% 0.00% 0.00% 22.67% HDO aromatics 12.02% 14.05% 11.53% 12.82% 10.51%Total saturated ketones 0.00% 0.00% 0.00% 0.00% 12.84% Total acids & esters 0.00% 0.00% 0.00% 0.00% 11.89% Total furans & furanones 0.00% 0.00% 0.00% 0.00% 0.00% Total tetrahydrofurans 0.00% 0.00% 0.00% 0.00% 3.28% guaiacols/syringols 0.00% 0.00% 0.00% 0.00% 18.91%straight-chain/branched alkanes 11.72% 13.62% 13.18% 10.32% 0.00% unknowns 5.49% 4.45% 5.62% 5.24% 0.00%

TOTAL 100.00% 100.00% 100.00% 100.00% 100.00% Hydrotreated

390°C, 1500 psig, 0.12-0.23 LHSVHydrotreated mixed wood bio-oil

Composition of Non-Isothermal Hydroprocessed ProductsHydroprocessed Products

Bio-oil Source C H O N S Moisture Density TANymixed wood 87.7 11.6 0.6 <0.05 0.01 0.07 0.84 1.6 oak 87.7 11.7 0.3 0.05 0.06 0.04 0.84 0.8 corn stover 87.4 11.9 0.4 0.40 0.005 0.06 0.84 2.5 poplar (hot-filtered)* 85.2* 10.2* 4.9* 0.14 0.19 0.51* 0.92* 6.1*poplar (hot filtered) 85.2 10.2 4.9 0.14 0.19 0.51 0.92 6.1

250-410°C, 2000 psig, 0.15 LHSV

* Use of a different, apparently less active catalyst

Total Acid Number (TAN) is still higher than most refineries would accept Further research on the complex issue of TAN and whichFurther research on the complex issue of TAN and which molecules initiate corrosion with respect to bio-oil products is required

Comparative Yields of Two-Stage Processing versus Non-Isothermal Processingversus Non Isothermal Processing

Hydro-treating

Hydro-cracking

HT/HC total

Non-isothermal

Mixed Wood dry oil yield g/g 0 62 0 61 0 37 0 50Mixed Wood dry oil yield, g/g 0.62 0.61 0.37 0.50 aqueous yield, g/g 0.48 0.24 0.63 0.48 C gas g/g 0.062 0.087 0.116 0.192 H2 consumption, L/L 205 290 385 710pCorn Stover dry oil yield, g/g 0.45 0.81 0.35 0.37 aqueous yield, g/g 0.61 0.14 0.67 0.64 C gas g/g 0.066 0.090 0.106 0.323 H2 consumption, L/L 76 490 296 490 Hot-filtered poplar dry oil yield, g/g 0.59 0.80 0.46 0.48 aqueous yield, g/g 0.46 0.17 0.56 0.46

C / 0 060 0 116 0 128 0 259 C gas g/g 0.060 0.116 0.128 0.259 H2 consumption, L/L 252 430 506 630

Distributed Pyrolysis and Centralized Bio-oil Processing

Corn StoverCorn Stover

Refin

ery

P P

P P

Refin

ery

P P

P P

StabilizationPyrolysisBiomass

Deoxygenate

GasolineDieselJet

Biocrude

P PP P

Mixed WoodsMixed Woods

JetChemicals

Other Refinery

Processes

Holmgren, J. et al. NPRA national meeting, San Diego, February 2008.

Performance Estimates for the Production of Naphtha and Diesel from Pyrolysis Oil

Wt%

Feed 100

H2 3-4.5

ProductsNaphtha Range 21

Diesel Range 21

Water CO Lights 60Water, CO2, Lights 60

Holmgren, J. et al. NPRA national meeting, San Diego, March 2008.

Gasoline Analyses From Two Step Hydroprocessing

Hydroprocessed Bio-oil (from Mixed Wood) PetroleumGasoline

Min Max Typical

Paraffin, wt% 5.2 9.5 44.2

Iso-Paraffin, wt% 16.7 24.9,

Olefin, wt% 0.6 0.9 4.1

Naphthene, wt% 39.6 55.0 6.9

Aromatic, wt% 9.9 34.6 37.7

Oxygenate, wt% 0.8

The carbon recovery based on bio-oil was about 50%.

Holmgren, J. et al. NPRA national meeting, San Diego, March 2008.

Gasoline/Diesel Prospects

Bioderived fuel from corn stoverspinning band distillation

54% in gasoline rangeIBP-193°C

35% in diesel range193-325°C

10-20% heavies>325°CIBP-193 C 193-325 C >325 C

Gasoline Octane numberRON+MON/2=89

Cetane number31.5

likely partiallyconverted feed

from: Timothy Brandvold UOP LLC “Pyrolysis Oil to Gasoline”

Deoxygenated bio-oil produces a high quality gasoline component, lower quality diesel and a jet blending component

from: Timothy Brandvold, UOP LLC, Pyrolysis Oil to Gasoline presented at the Thermochemical Portfolio Alignment and Peer ReviewApril 15, 2009, Denver, CO http://obpreview2009.govtools.us/thermochem/documents/UOP_Project.PyOilGasoline.Final.pdf

Vacuum Distillation Curves for Hydroprocessed Bio-oil

70

80

90

50

60

70

istil

led

batch 1

44.2% 42.4%

30

40

perc

ent d

batch 1batch 2

naphtha

jet

0

10

20ap a

00 50 100 150 200 250 300 350

temperature, degrees Celsius (corrected to 1 atm)

Cost Estimates for the Production of Naphtha Range and Diesel Range FuelsNaphtha Range and Diesel Range Fuels from Pyrolysis Oil

From Wood

From Corn Stover

DOE 2012 BC Target

Total Cost $/gal, Produced 2.50 2.82 2.62*

Total Cost $/gal EtOH equivalent 1.55 1.74 1.76*

Gallon of EtOH Equivalent/ton 120 87 89.9qbiomass

% Carbon recovery 44 36 34.5

All cases based on 2007$, $46/ton biomass, $100/bbl fuel value ($2.38/gallon), 10% ROITimothy Brandvold, UOP LLC, “Pyrolysis Oil to Gasoline” presented at the Thermochemical Portfolio Alignment and Peer Review, April 15, 2009, Denver, CO * Annual Energy Outlook 2009, March 2009, DOE/EIA-0383(2009)* Biomass Program Multi Year Program Plan, May 2009

cases based o 00 $, $ 6/to b o ass, $ 00/bb ue a ue ($ 38/ga o ), 0% O

Conclusions

Biomass conversion to liquid fuels via pyrolytic processes q py y pand catalytic hydroprocessing is under development.Interesting yields of hydrocarbon liquid products have been demonstrated at the bench-scale.been demonstrated at the bench scale.Improved understanding of process steps and product properties is developing.P i i i i th t iProcess economics are promising in the current economic environment.Scale-up is envisioned in the near term.p

Mild C t l ti H d t ti f BiMild Catalytic Hydrotreating of Biomass Pyrolysis Oils to Produce a Suitable

Refinery FeedstockRefinery Feedstock

tcbiomasss2009

Richard J. FrenchJason HrdlickaRobert Baldwin

S t b 18 2009September 18, 2009

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

Pyrolysis Oil Fuel PropertiesH

Property Bio‐oilHeavy Fuel Oil

Moisture Content, wt% 15‐30 0.1

pH 2 5pH 2.5 ‐‐

Specific Gravity 1.2 0.94

Elemental Composition, wt%

C 54‐58 85

H 5.5‐7.0 11

O 35‐40 1.0

N 0‐0 2 0 3N 0 0.2 0.3

Ash 0‐0.2 0.1

HHV, MJ/kg 16‐19 40

Viscosity (at 50 °C), cP 40‐100 180

Solids, wt% 0.2‐1 1

Distillation Residue Up to 50 1

• Corrosion, erosion of diesel injectors, • soot formation

National Renewable Energy Laboratory Innovation for Our Energy Future

• soot formation• total acid number > 100 mg KOH/g oil

Czernik&Bridgwater, E&F 2004

Hydrodeoxygenation of Pyro Oil

Hydrodesulfurization, hydrocracking, hydroprocessing, and hydrotreating are standard petroleum techniquesy g p q

Becoming more intense as sulfur standards in gasoline and diesel are being lowered to 15ppm and the quality of crude oil is decreasing

Hydrodeoxygenation of bio-oil uses similar catalysts and conditions, yields oils with improved properties

Studied at PNNL, U. Louvain, and others


Two-Stage Hydroprocessing

• Fast pyrolysis, poplar• Laboratory Dual-trickle-bed reactory• Downflow better than upflow• Lower hydrogen consumption

150/350-380°C, Ni-Mo/Al2O3

SLHSV 0.28-0.43Yield g/g feed 0.38-0.53Oxygen wt% 0 5 2 0Oxygen wt% 0.5-2.0Density 0.82-0.86

Elliott&Neuenschwander, Dev.Therm.Biom.Conv. 1997


Techno-Economic Studies

• Baldauf et al. Veba (1994) concluded not economic- Low product yieldsp y- High hydrogen consumption- Low quality products that will need further upgrading

Corrosion- Corrosion

• Marker et al. UOP (2005)Acid is “most serious problem”- Acid is most serious problem

- High hydrogen consumption makes it “unlikely to be commercially viable”

• Jones et al. PNNL (2009)- Costs very close to program targets


Refinery-Oriented Analysis

• Jones et al. Refining cost too high- $40/bbl vs. $4-12/bbl

• Increasing scale to 20,000bdmtpd $22/bbl

• w/ Partial upgrading and blending(increase oxygen from 0 2% up to 7%) $12/bbl(increase oxygen from 0.2% up to 7%) $12/bbl

NREL Subcontract


Partial Upgrading ScenariosREFINERY

PYROLYSIS DISTILLATIONLOW-ACID PYROLYSIS DISTILLATION TOWER

T

CRUDE

INTERNAL STREAMS

TRUC

8:1

STREAMSCK

PARTIAL HYDRO-

PROCESSINGPRODUCT BLENDINGPIPELINE, BARGE, TRUCK

.


Global Energy Management Institute

Refinery Analysis--Recommendations

• Consider using partially upgraded pyrolysis oil containing ~7% oxygen as a refinery co-feedcontaining 7% oxygen as a refinery co feed

• Evaluate for key refinery parameters- Acidity a “show stopper” for carbon steel- 100% miscibility with petroleum- Adequate volatility (distillation tower or internal

fi t )refinery streams)• Other parameters

- pH - catalyst poisons- pH - catalyst poisons- compatibility - other fuel spec’s- thermal fouling - form of oxygeng yg

NREL subcontractNational Renewable Energy Laboratory Innovation for Our Energy Future

Objectives

• Carry out Catalytic Hydrotreating with variable severity conditions (Temperature and Time)y ( p )

• Investigate Relationship betweenTAN and pHTAN and Total OxygenTAN and Total OxygenTAN and Oxygen Functional Groups

Aldehydes, ketones, acids, alcoholsOxygen Content and Oil StabilityOxygen Content and Oil StabilityOxygen content and solubility in hydrocarbons

• Identify maximum oxygen content for completesolubility with acceptable TAN and volatility andsolubility with acceptable TAN and volatility and make 0.5L of that composition for further refinery testing


Experimental—Reactor

Trickle bed:• Similar to industrial

Batch Reactor*:• Catalyst slurry All• Similar to industrial

• Traps contaminants

• Catalyst slurry--All catalyst exposed, changes conversioncontaminants

• Slow equilibration• Long runs

changes conversion and deactivation

• Short experiments• Long runs p

Either is suitable for conditionsEither is suitable for conditions• Up to 450°C• Up to 3000psig


Up to 3000psig

*Gagnon&Kaliaguine, I&ECR 1988

Hydrotreater System Schematic1 lit S ib t h R t

1-L Hydrotreating reactor operation schematic

JH 6/26/09

3

V E1

HV-E5

cwr

1-liter Semibatch Reactor

vent

gasbag

He(2500 psi)

PC-A4

1

V-F3F

FC-A2

CV-A1

2

FC-A1

HV-S2

HV-S3 V-S14

V-E1

V-E2

HV-E1HV-E21

cws

sample valve withextended handle

NC

bag

FCS-C2

HV-F4PCS-F1

HV-E3

PC-E1

PI-E1P

LELAIT-H1

P

PC-C3PC-C2

FCS C2SV-C2 CV-C2

CV-C3

HV-C3HV-K1

HV-K2FC-K3

C K3 HV K4

1

2

HV-A13

4

PI-K1

HV-C2 HV-E4

PP

PT-M1PI-M1

cws

cwrHV-A2

condenser samples 1-5

He(6000 psi)

H2(3500 psi)

EN-C1 HV-M1

H-M1V-M1

EN-K1

C-K3

HV-K5

FC-K6

HV-K4

V-SAMPLE

air

air to vent

SV-D1

HV-D1


separate enclosuremounted to fume hood

Gas cabinet

Fume hood

EN-H1

air

Experiment Plan

Conditions• First Stage150 280°C• First Stage150-280 C• Second Stage 300-400°C• Total Pressure 2000-2500psi hydrogen

H d fl 0 l


• Hydrogen flow 0-5slm• Sample slurry product and condensate

Catalyst • NiMoSx/Al2O3,

GraceMill 200/ 400

F vent

Hydrotreating catalyst sulfidation schematic

JH 4/10/09

NC

dragertube

FC-S4HV-S1

• Mill to +200/-400• Sulfidation

1 Room T-100°C

P

tube

scrubber

CV-S4 SV-S4

PT-S3HV-S2V-S2

TE-S1

PC-A4

He

1. Room T 100 C, 10°C/min, He

2. 100°C-Final T 0 3 1°C/ i

F

Heater

NC

FC-S3

HV-S3

V-S1

H-S1TE-S2TES-S3

HC-S1

PC-S1 SV-S3

0.3-1°C/min5%H2S/H2

50-100sccmgas cabinet

Heater contains a quartzcatalyst housing 2.5 cm diameter

and 23 cm length

fumehoodEN-S1

EN-S2

5% H2S/95% H2

3. Test for H2S breakthrough4. Cool rapidly under H2S

• Transfer under Helium• Transfer under Helium


Feedstock

• Pyrolysis Feedstock Biomass: White Oak• Pyrolysis Reaction Conditions• Pyrolysis Reaction Conditions

T = 500 °Cresidence time ≈ 0.5 sentrained-flow TCUF pyrolysis reactor

• Elemental Analysis, Pyrolysis Oil Feed (wt%)

Water Ash S C H N O24.6 .06 .019 42.8 4.7 <.01 27.9

• Carboxylic Acid Number (CAN)* = 83

*Nicolaides, G.M. (1984), Carboxylic acid measurement


Results—Oxygen ContentExp't

#Temperature

(°C)H2 flow

(slm)Cat/Feed

time (h)

Pressure (psig)

Oxygen MAF (wt%)

280 0 3 1 1 2000 19

1

280 0.3

9

1.1 2000 19320 0.3 0.6 2000 16340 0.4 0.3 2000 12360 0.5 0.4 2000 13

2 280/340 0 10 1.4/3.2 2500 138* 150/340 1.0 10 1.0/1.0 2500 7.37* 150/360 1.0 15 1.0/1.0 2500 7.09* 150/360 1 5 11 1 0/1 0 2500 7 69* 150/360 1.5 11 1.0/1.0 2500 7.66* 150/380 1.0 14 1.0/1.0 2500 7.83* 150/400 2.0 14 1.1/2.5 2500 5.04* 150/400 3 2 15 1 1/2 5 2500 2 4

*Condenser sample

• Maximum temperature appears to be dominant variable

4 150/400 3.2 15 1.1/2.5 2500 2.4


p pp• Condensate dominates above 360°C• Reaction is fast at 400°C & slower at 360-380°C

Properties of Major Organic PhaseTempera

-ture(°C)

Oxygen MAF (wt%)

CAN (mgKOH

/g)

PAN (mgKOH

/g)

Volatiles MAF (wt%)

SolubilitySpec. Grav.

Vis-cosityH T Ac

Feed 28 83 69 67 I I VS >1 mod.280 20 62 I SS VS >1 high320 16 85 I I VS >1 high340 12 66 80 I SS VS >1 high340 12 66 80 I SS VS >1 high360 13 61 78 VS VS VS ~1 high

280/340 13 67 87 ~1 high*150/340 7.3 <1 35 VS VS VS <1 low*150/360 7.0 <1 21 VS VS VS <1 low*150/360 7.6 <4 30 VS VS VS <1 low*150/380 7.8 <1 22 VS VS VS <1 low*150/400 5 0 <2 13 100 VS VS VS <1 low150/400 5.0 <2 13 100 VS VS VS <1 low*150/400 2.4 <2 12 97 VS VS VS <1 low

*Condenser productI=Insoluble, SS=Slightly soluble, S=Soluble (10-50%v/v),


, g y , ( ),VS= Very soluble (>50%v/v)CAN=Carboxylic acid number, PAN=Phenolic acid numberNicolaides 1984

Comparison with Aqueous Phase

Organic AqueousTempera-ture (°C)

Oxygen MAF (wt%)

CAN (mgKOH/g)

Carbon (wt%)

CAN (mgKOH/g)ture ( C) MAF (wt%) (mgKOH/g) (wt%) (mgKOH/g)

280 20 62320 16 7.9340 12 66 none360 13 61 4.4 122

280/340 13 67 7.7*150/340 7.3 <1 5.5*150/360 7 0 1 4 1 4*150/360 7.0 <1 4.1 <4*150/360 7.6 <4 5.3 2*150/380 7.8 <1 4.9 <1*150/400 5 0 <2 2 7

* = condenser sample

150/400 5.0 <2 2.7*150/400 2.4 <2 2.7


• low T and flow, acid is extracted into the aqueous phase• Carbon in the aqueous phase tracks oxygen in the organic phase

Volatility-Microdistillation

• BR Instruments 8T spinning-band still, 10ml.p g ,• Sample foamed badly, some losses: results

normalized• Experiment 9, 360°C, 2500psig, 1.5slm H2

• High yield of naphtha is promising

Fraction Yield (wt%)

Temperature (°C)

Pressure (kPa)

AET (°C)

Initial BP 77 82 84Initial BP 77 82 84naphtha 57 111 8 193kerosine 27 180 8 271gas oil 9 135 0.1 328


resid 7

Reaction Selectivity and Product Quality, 360 °C

Carbon Conversion Based on FeedCondensate oil = 36%Condensate oil 36%Heavy oil = 30%Water-soluble organics = 6.4%gGases (CO, CO2, C1, C2, C3) = 12%Residue = 5.1%Product at 360 °C Ultimate Analysis (wt%)

C H N O S

Atomic H/C ratio ≈ 1 7 1 5

77 11 0.14 7.6 0.0883 10 0.13 3.7 0.35

Atomic H/C ratio ≈ 1.7, 1.5


Hydrocarbon Type AnalysisGC/MS of Volatile Organic CondensateAlkanes

C6, C7, C8, C9

Alkyl Substituted CycloparaffinsC l t l hCyclopentanes, cyclohexanes

Unsaturatesindenes cyclohexenesindenes, cyclohexenes

Aromaticsalkylbenzenes, methoxybenzenes, toluene, naphthalenes, PNA’s

Phenol and Alkyl PhenolsOther Oxygenates

Pentanones, hexanones, hexanols, furans


Summary

Hydrodeoxygenation should be more affordable if several percent of the oxygen is allowed toseveral percent of the oxygen is allowed to remain in the product

Refinery-relevant oil properties at partial y p p pdeoxygenation are needed to determine what level of upgrading is needed to meet refinery t d dstandards

New results show that a higher-oxygen oil can have low acidity good volatility and good miscibilitylow acidity, good volatility, and good miscibility

Produced 0.5L of oil with 7% oxygen for further analysisy


Future Work

• Improve measurement of hydrogen consumptionp y g p• Reduce residual liquid• Zero in on “sweet spot”• Carry out detailed physico-chemical characterization

elemental, TAN, pH, hydrocarbon types, oxygen functional groups, density viscosity solubility in HC volatility (simulated distillation)density, viscosity, solubility in HC, volatility (simulated distillation)

• Investigate use as refinery blendstock (GEMI, Valero)


Acknowledgements

Bob Baldwin Stuart BlackJason HrdlickaJason Thibodeaux

Michele MyersBill Michener

Stefan Czernik Jim Stunkel

Tom FoustDOE Office of the Biomass ProgramDOE Office of the Biomass Program


Mild C t l ti H d t ti f BiMild Catalytic Hydrotreating of Biomass Pyrolysis Oils to Produce a Suitable

Refinery FeedstockRefinery Feedstock

tcbiomasss2009

Richard J. FrenchJason HrdlickaRobert Baldwin

S t b 18 2009September 18, 2009

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

Lignin valorisation for chemicals and (transportation) fuels via (catalytic) pyrolysis and hydrodeoxygenation

Paul de Wild, Ron van der Laan, Arjan Kloekhorst and Erik Heeres

Outline

• What is lignin; why and how to valorise it?g y

• Experimental

• Results

• Conclusions, Challenges, Outlook

224-9-2009

Wh t i li i ?• Biopolymer, consisting of

randomly linked phenylpropane units

What is lignin?

• ‘Glue’ that –in a sort of two-component mixture with hemicellulose- holds the cellulosic wood-structure together and protects it against microbial threats. The ghemicelluloses act as coupling agents between the lignin and the cellulose.

• Biogenesis from glucose via the enzymatic Shikimic acid pathway to p coumarylpathway to p-coumaryl , coniferyl and sinapyl alcohol followed by random (non-enzymatic) polymerisation of these aromatic alcohols.

• Very complex structure thatVery complex structure that depends on plant species and growth conditions. Exact structure and structure –function relationships not known yet.

D Meier 2006

324-9-2009

D. Meier, 2006

Simplified molecular structure of ligninSimplified molecular structure of lignin

guaiacyl-unitg y

• Most internal lignin bonds via the para position

• Approx. 50% of all bonds are

424-9-2009

syringyl-unitpp

of the β-O-4 type

Main components lignocellulosic biomassMain components lignocellulosic biomass

Deciduous woods

40-50% cellulose30-40% hemicellulose

Coniferous woods


Herbaceous crops


20-25% lignin(syringyl & guaiacyl units)

30-35% lignin(mainly guaiacyl units)

15-25% lignin(p-hydroxyphenyl, guaiacyl & syringyl units)

524-9-2009

Lignin valorisationWhy?– Lignin is worlds second / third most abundant natural polymer– Lignin is worlds second / third most abundant natural polymer– Lignin contains many valuable aromatic (phenolic) structures– Lignin is the main constituent of large residual streams from e.g. the pulp and paper

industry and – increasingly- biorefineries for bio-EtOH– Lignin in itself is a valuable resource for many performance products

How?– Combustion for heat and/or power (only practised option to date)– Gasification for syngas – Hydroliquefaction for transportation fuels (reformulated gasoline)– Pyrolysis for chemicals (monomeric phenols) and/or performance products

Succesful valorisation of lignin is a key-issue for an economic viable lignocellulosic biorefinery!

624-9-2009

Multi-product biorefinery incl. lignin upgradingPrimary biorefinery Secundary biorefinery

Chemical derivatives, e.g. surfactants

Hemi-Cellulose Conversion

& synthesis Furfural

Pretreatment

&

Pretreatment &

fractionation

Lignocellulosic biomass &

residual streams

EthanolButanol

Lactic acidPropanediol

Cellulose Hydrolysis

synthesis

Fermentation

Levulinic acid

fractionation

Lignin

Lactic acid

Thermochemicaldepolymerisation & conversion

Platform chemicals, e.g. phenolics, styrene,…Performance products

CombustionElectricity

Heat

Fuel additives

724-9-2009

S li ti f li i d i d h liSome applications of lignin-derived phenolics...’Green’ plastics Bio-bitumen for

asphalt and otherWood-adhesives and resins

asphalt and other building materials

Specialty phenolics for high-value applications such as

fragrances and pharmaceuticals

824-9-2009

fragrances and pharmaceuticals

E i tFeedstocks– Alcell organosolv lignin from mixture of hardwoods

Experiments

g g– Granit Asean lignin from straw / sarkanda grass

Thermal characterisation – Fusion tests

Crushed solidified lignin melt

– Thermogravimetric analysis (DSC / TGA)

Production of feedable particles– Slurrying with water,melting, solidificationS u y g t ate , e t g, so d cat o

crushing, sieving into < 2 mm particles– Pelletising

Pyrolysis tests in bubbling fluidised bed reactor ‘The WOB’y y g

Hydro-deoxygenation trials in pressure vessel

924-9-2009

Al ll th l h t i ti F i t t f 1 Al ll li i d i iAlcell thermal characterisationFusion test– Moisture loss up to 4 wt%

Fusion test of 1 g Alcell lignin powder in air

92%

94%

96%

98%

100%Open circles estimated from TGA results

– Melting at approx. 180 °C– Weight loss ~ 8%– 17 % wt loss at 220 °C

TGA / DSC 80%

82%

84%

86%

88%

90%

Wt %

TGA / DSC– Significant wt loss starts at 200 °C– Max rate of degradation at 360 °C

At 500 °C still 45 wt% residual ligninTGA Alcell lignin in N2 100-500°C

120 2

80%20 40 60 80 100 120 140 160 180 200 220 240

Temperature (°C)

– At 500 C still 45 wt% residual lignin– Thermoplastic behaviour in between

150°C – 200°C with a clear endothermic DSC signal around 174°C (not shown) 60

80

100

120

d w

eigh

t los

s (%

)

1

2

AT (m

g/m

in)

0

20

40

0 50 100 150 200 250 300 350 400 450 500

Temperature (°C)

Nor

mal

ise

0

AW

/A

1024-9-2009

Temperature ( C)

Bubbling fluidised bed pyrolysisBubbling fluidised-bed pyrolysis– Hot sand-bed, 400-500°C,

fluidised with Ar– Vapour residence times (seconds), apou es de ce t es (seco ds),

solid residence time (minutes)– Product collection by CEN/TS tar

sampling protocol, using washing bottles. For continuous experiments sampling by cooledexperiments sampling by cooled condensers and an ESP

– On-line analysis of non-condensable gases

– Off-line analysis of condensable d t b GC/MS/FIDproducts by GC/MS/FID

1124-9-2009

VentNitrogen

CycloneBubblingfluidised

bed reactor

Manually or screw operated feed bunker

Freeboard

Product gas sampling

Cyclone ash collection bin

B bbli

Lignin feed

Cooled feeding screw

Heated soxhlet particle filter

Bubblingfluidised hot sand

bedContinuoustests

Argon and/or nitrogen fluidisation gas

Heater

ESP

Coolant

Batch tests

Tar sampling system consisting of

6 isopropanol filled impinger bottles, designed

to trap both aerosols and d bl Pump

+40°C

Pump

tests

1224-9-2009

condensable gas Pump

-20°C Pyrolysis product obtention test rig with room temperature condenser, elektrostatic

filter and freeze condenser

Temperatures and gas evolution during pyrolysisTemperatures and gas evolution during pyrolysisAllcel organosolv lignin pyrolysis at 400 °C in a bubbling fluidised bed

480

500

1 8

2WOB_TI_3_2

WOB TI 3 3

440

460

480

1.4

1.6

1.8

.%

WOB_TI_3_3

WOB_TI_3_4

WOB_TI_3_5

WOB_TI_3_6

WOB CO

400

420

T / °

C

1

1.2

cent

ratio

n / V

ol WOB_CO

WOB_CO2

WOB_CH4

5th onset of bed defluidisation due to agglomeration

340

360

380

0.4

0.6

0.8

Gas

con

1st portion fed3rd

4th

6th (last)

300

320

340

5 7 9 1 3 5 7 9 1 3 5 7 9 1 3 5 7

0

0.2

0.42nd

1324-9-2009

14:15

14:17

14:19

14:21

14:23

14:25

14:27

14:29

14:31

14:33

14:35

14:37

14:39

14:41

14:43

14:45

14:47

Lignin pyrolysis degradation productsMonomeric phenols from the thermal degradation of

Approx. 60% of GC-detected compounds not (yet) identified

At 400 °C 3-4x as much phenolics when compared to 500 °C Main phenolics at 400

Monomeric phenols from the thermal degradation of Alcell organosolv lignin in a bubbling fluidised bed at 400 °C - 500 °C

0 8

1.0

d (w

t% d

.b.)

400 °C, semi-continuous feeding of particles from crushed solidified lignin-melt, total yield phenolics = 2.5 wt%, mass balance 85%

500 °C, batch feeding of particles from evaporated and crushed lignin-EtOH slurry, total yield phenolics = 0.7 wt%, mass balance 71%

500 C. Main phenolics at 400 °C: guaiacols, syringols. At 500 °C more phenol and catechol.

Incomplete conversion due to feeding problems

0.6

0.8

Prod

uct y

iel

to feeding problems (agglomeration and bed defluidisation)

0.2

0.4

0.0

Guaiacol

Methyl-g

uaiacol

Phenol

Eugenol3-Ethylphenol

Syringol

IsoeugenolPyroca

techol

Syringaldehyde

Hydroquinone

4-Me 3 Sy H

1424-9-2009

Batch pyrolysis results; screw tip deposits andBatch pyrolysis results; screw tip deposits and reactor bed agglomeration

Bottom-up view through reactor tube, showing agglomerate at the feed inletshowing agglomerate at the feed inlet port

Spent bed material containing large char – sand agglomerateschar – sand agglomerates

1524-9-2009

Bubbling fluidised bed fast pyrolysis of herbaceous lignin at 400°C - 500°C

Catalytic pyrolysis

Non-catalytic pyrolysis

Improving thermal degradation by application of a catalyst

of herbaceous lignin at 400 C 500 C

4

5

y fe

edst

ock

Non catalytic pyrolysis

3

ield

in w

t% d

ry

1

2

Pro

duct

y

0Methanol Guaiacols Syringols Phenols Catechols

1624-9-2009

C ti t l ti l i t tContinuous catalytic pyrolysis testsSuccessful continuous Alcell and Granit lignin pyrolysis trials with cooled screw and low feeding rate (150 g/hr) to minimise melting behaviour.

Pyrolytic y ylignin-oil fromAlcell lignin

Freeze condenser fraction from

ESP fraction from captured aerosols

fraction from low-boiling point

components

1724-9-2009

captured aerosols

R lt ti t t20

eld

(wt%

d.b

.)

PhenolsResults continuous tests

100 lignin pyrolyses to: 17 - 20 gas (CO, CO2, CH4)

15

Yi Catechols

Guaiacols

2 420 - 25 water13 - 20 organic condensables30 - 35 solid (char)Th li id d t h b ll t d i

10Syringols

The liquid product has been collected in two fractions, a thick, homogeneous oily liquid with an aromatic smell and an aqueous fraction with a pungent smell.

5GC-detected,unidentifiedphenols

Oligomeric

The pyrolytic lignin oil was subjected to a HDO trial at RUG

0Deciduous biomass

derived ligninHerbaceous biomass

derived lignin

Oligomericunknownphenols

1824-9-2009

g g

Duplicate continuous pyrolysis of Alcell ligninDuplicate continuous pyrolysis of Alcell lignin1000

Tube (400 --> 25 °C) ESP (25 °C) Cooler (-30 °C)ESTD Wt% d.b.

Phenolics 6.4Others 3.0Water 13.6

600

800 Oligomers 8.0Total 31.1

400

g/kg

0

200

0Moisture Phenols identified Others Unknowns Undetected

Main product yields 1st experiment: 20 wt% gas, 37 wt% oil, 35 wt% char, balance 92 %Main product yields 2nd experiment: 13 wt% gas, 32 wt% oil, 44 wt% char; balance 89 %Main uncertainty is the amount of char, higher char yield might be due to longer vapour residence time when compared to the 1st trial

1924-9-2009

residence time when compared to the 1st trialTube and ESP sample to be treated by HDO at RUG (ongoing)

Lignin thermal degradation mechanism hypothesisLignin thermal degradation mechanism hypothesisPermanent gases & water (CO, CO2, CH4, H2O)

LigninMonomeric phenols

Condensation / degradation

degradation

CatalystLigninPyrolysis Oligomeric phenols

Condensation

Melting

CharFor a maximal conversion of lignin into (monomeric) phenols there is a narrow window of pyrolysis conditions such as temperature, heating rate, vapour and solid residence time.

First of all a proper feeding procedure is required to overcome lignin’s thermoplastic behaviour that causes severe operational problems such as screw feeder clogging by molten lignin, agglomeration and subsequent defluidisation of the reactor bed.

2024-9-2009

Application of proprietary catalysts.

Hydrodeoxygenation of pyrolytic lignin oilHydrodeoxygenation of pyrolytic lignin oilConditions• 350 oC350 C• 100 bar H2

• 1 h reaction time• Stirring rate 1500 rpm• 2 g PLO• 30 ml dodecane• 0.2 g Ru/C catalyst

Al ll d i d l ti li i il• Alcell derived pyrolytic lignin oil• Batch mode operation

Analysis• 2D-GC

• GC-MS

2124-9-2009

P l ti li i il i t di t lPyrolytic lignin oil as an intermediate low moleculair weight compound for HDO• Alcell lignin has a high molecular weight (≈ 2200 g/mol ) is difficult to depolymerizeAlcell lignin has a high molecular weight (≈ 2200 g/mol ), is difficult to depolymerize

and harder to correlate to model compounds.• Pyrolytic lignin oil has a much lower molecular weigth ( ≈ 800 and 1000 g/mol) and is

a good intermediate between model compounds and pure lignin3,0

2,0

2,5

ECN PLO Alcel Lignin Pyrolytische lignin

GPC of intermediate low

1,0

1,5moleculair weight lignin:Original Alcell ligninPyrolytic lignin oil

10 100 1000 10000 100000

0,0

0,5

2224-9-2009

10 100 1000 10000 100000

Molmass

HDO results for Alcell derived pyrolytic lignin oil (PLO)

20 Pyrolytic lignin oil HDO pyrolytic lignin oil

14

16

18

wt%

)

8

10

12

cent

ratio

n (w

2

4

6Con

c

Alkylphenolics Catechols Alkanes Guaiacols Cyclohexanols0

2

Extensive hydrogenation of phenolic compounds to alkanes and cyclohexanols!

2324-9-2009

te s e yd oge at o o p e o c co pou ds to a a es a d cyc o e a o s

11H-NMR PLO and HDO oil

PLO

HDO oil

ppm012345678910

2424-9-2009

0.4

G i l & S i l

0.3

0.35

io

Guiacols & Syringols

PLO

0.2

0.25

/C Atomic Rati

Alkyphenolics

0.1

0.15O/

Benzenes

Cycloalkanes

HDO oil0

0.05

0 0.25 0.5 0.75 1 1.25 1.5 1.75 2 2.25 2.5

Benzenes

2524-9-2009

H/C Atomic Ratio

Moleculair weigth after HDO treatmentMoleculair weigth after HDO treatment

3,0ECN HDO

2,0

2,5

ECN HDO ECN PLO

1,0

1,5

0 0

0,5

1,0

10 100 1000 10000 100000

0,0

MolmassNo depolymerisation of the larger fragments in the PLO!

2624-9-2009

No depolymerisation of the larger fragments in the PLO!

Conclusions– Under BFB intermediate pyrolysis conditions, lower pyrolysis temperatures result in

higher yields of phenolics in the range 400°C – 500°C. Half of the amount of GC-detected phenols is not identified yet and the amount of unknown and GC-

Conclusions

detected phenols is not identified yet and the amount of unknown and GCundetectable species is at least equal to the amount of detected phenolics. Assuming that the fraction undetected is of oligomeric phenolic nature, the total yield of phenolic substances is 13 – 20%.

– Smooth and continuous feeding of the lignin is extremely difficult due to melting and subsequent agglomeration causing defluidisation and clogging of the reactor bed but application of a specific promoter / catalyst significantly improves the lignin feeding b h i d i ld i t l t i th t f i h l (7 10behaviour and yields approximately twice the amount of monomeric phenols (7 – 10 wt%) when compared to the non-catalytic approach.

– Catalytic HDO treatment with with Ru/C as catalyst does not result in y ydepolymerization of PLO but causes a total hydrogenation of PLO towards cyclohexanols and alkanes. Apparently, HDO process conditions are too severe.

2724-9-2009

Challenges and outlookChallenges and outlookImproving feeding behaviourImproving thermal degradation and product collectionTest ‘home-made’ winter wheat straw organosolv ligninTechno-economic evaluationsFurther HDO tests with other catalyst under less severe conditionsFurther HDO tests with other catalyst under less severe conditions

Succesful pyrolysis experiment with ECN organosolv straw - lignin; products are currently analysedproducts are currently analysed

2824-9-2009

Acknowledgements

Dutch Ministry of Economic Affairs; SenterNovem for financial support

Acknowledgements

Ruud Wilberink, Gertjan Herder, Marco Geusebroek, Ben van Egmond and Karina Vogelpoel for technical assistance

Richard Gosselink of Wageningen University Research for providing the Alcell lignin

Prof. Tony Bridgwater of Aston University for providing the Asean lignin

2924-9-2009

Thank you for your attention!Thank you for your attention!Contact: Paul de Wild, [email protected], Tel.: ECN: +31 (0) 224564270, Mobile: +31 0610520901

Catalytic pyrolysis / HDO ?

Li iMonomeric

3024-9-2009

Lignin phenols

Integrated Hydropyrolysis and Hydroconversion (IH ) Process for Production of Gasoline and Diesel

2

Fuel from Biomass

Terry Marker, Larry Felix, Martin Linck - Gas Technology InstituteSept 18, 2009p ,

AgendaAgenda

>BackgroundBackground> Integrated Hydropyrolysis and Hydropyrolysis (IH2)>Proof of Principle Experiments>Proof of Principle Experiments>Process Comparison>Economics>LCA>Conclusions

Footer goes here2tcbiomass2009

Potential For U.S. Liquid Fuels from Lignocellulosic FeedLignocellulosic Feed

14

MMBPD

8

10

12

4

6

8

domestic

foreign

0

2

Transportation Potential from Potential from Fuels Vegetable Oil LignoCellulosic

Based on Billion ton per year of biomass and 28wt% conversion to liquid


Challenges for Pyrolysis or P l i Pl U diPyrolysis Plus Upgrading

>Undesirable Pyrolysis Oil Properties>Undesirable Pyrolysis Oil Properties > Limited demand> Expensive to transport> Incompatible with oil refinery metallurgy> Incompatible with oil refinery metallurgy

>Expensive Upgrading to Make Fungible Fuels> High H2 requirements> Severe conditions required in upgrading ( low LHSV and high pressure) result in an expensive upgrading process


Pyrolysis Oil PropertiesFast Pyrolysis Oil

% Oxygen ( including water) 50 (40% mf)% Water 20Total acid number (TAN) 200Stability PoorC4- 430°F Non-distillable430 - 650°F Non-distillable650°F+ Non-distillableCompatibility with crude oil or refinery products No, forms separate phaseHeating value BTU/lb 6560Heating value, BTU/lb 6560Transportation cost highPolynuclear Aromatics significant


Pyrolysis Oil Upgrading Requirementsy o ys s O Upg ad g equ e e tsPyrolysis Oil Upgrading Consequences

H Use 3 4 t% Hi h osts h rts LCAH2 Use 3‐4 wt% High costs, hurts LCA

LHSV .15‐.3 High catalyst and capital costcost

Pressure psia 1500‐2500 High capital cost

Feed TAN 200 Can’t be run in current refinery hydroconversionrefinery hydroconversion units designed for metallurgies with TAN < 2

Wt% Liquid hydrocarbon 25‐30% Understandable sinceWt% Liquid hydrocarbon product from starting biomass

25 30% Understandable since starting feed 50% oxygen

A fundamentally better approach is needed


y pp

IH2 Processing Approach>Avoid all the problems associated with upgrading

and stabilization of pyrolysis oil, by using a hydropyrolysis first step to making a feed which ishydropyrolysis first step to making a feed which is easier to upgrade in a second integrated hydrotreating step y g p

>Design a system with maximum process integration which also requires no external hydrogenq y g

>Removing oxygen from molecules can be done stably at moderate hydrogen pressure for many y y g p ybiomass structures

>US Patent #7,511,181 teaches good catalyst stability for deoxygenation at 250psi for lipids


deoxygenation at 250psi for lipids

Integrated Hydropyrolysis and H d i P IH 2Hydroconversion Process IH 2

• Directly make desired products• Run all steps at moderate hydrogen pressure (200-500 psi)• Utilize C1-C3 gas to make all H2 required

A id ki “b d ff” d i l i PNA f di l


• Avoid making “bad stuff” made in pyrolysis – PNA, free radicals

IH2 Proof of Principle Pilot Plant Unit


GTI IH2 Equipment

• H2 pressures 200-500psi• Fast heat up of continuously fedFast heat up of continuously fed

biomass• Specially designed feeder• Well fluidized bed of catalyst for

h d l ihydropyrolysis• Bed shows no sign of

agglomeration • Hot internal filter shows no signsHot internal filter shows no signs

of coking or pressure buildup• Integrated fixed bed hydro-

treating – using CRI/Criterion Inc C M t l tCoMo catalyst

• Hydrocarbon product floats on top of separate water phase


GTI IH2 Proof of Principle Experimental Resultsp

Test 1

Feedstock WoodFeedstock Wood

HC Liquid Yields wt% 24‐28%

% Oxygen in Liquid <1%

% Gasoline + Diesel in liquid product 100%

% char 10

% CO 14% COX 14

% C1‐C3 14

% H2O 33

% C in water phase 0.2%

Further optimization of conditions and yields likely


Further optimization of conditions and yields likely

Product Property ComparionsFast Pyrolysis Oil IH2 product

% Oxygen 50 <1.0%

% Water 20 <0.1%

TAN 200 <2

Stability Poor Good

H ti V l Bt /lb 6560 18000Heating Value Btu/lb 6560 18000

% C4‐ 650° F Non‐distillable 99+

% 650° F + Non‐distillable <1

Compatibility with crude oil or refinery products

No Excellent

Relative transportation 1.0 0.3cost

It’s a lot easier to find a market for desirable products than undesirable ones


Recipe for H2 Self SufficiencyRecipe for H2 Self Sufficiency

1 Utilizing the C1-C3 gas for making H2 in steam1. Utilizing the C1 C3 gas for making H2 in steam reformer ( usually burned in pyrolysis)

2. Balanced COX and H2O production in the IH2

process with catalyst and conditions:• Too much H2O production uses too much H2• Too much COX reduces liquid yieldsToo much COX reduces liquid yields • After water gas shift H2O/CO2 =1.0

3. Water Gas shift in hydroconversion reactor to make in situ hydrogen from water CO + H2O CO2 +H2


Technology ComparisonTechnology ComparisonFast Pyrolysis Distributed Pyrolysis +

UpgradingIH2

Product properties Poor Excellent Excellent

External H2 required None 3‐4% None

C i l di i h diCapital costs Medium High Medium

Hot filtering Difficult Difficult Straightforward

Heat of reaction Mildly Pyrolysis =Mildly Both Stages very endothermic* endothermic*

Upgrading =very Exothermic

Exothermic

Integration ith None No YesIntegration with upgrading

None No Yes

Transportation costs Medium High Low

Footer goes here14tcbiomass2009 * Literature reports pyrolysis as both mildly endothermic and mildly exothermic

Mild Hydroconversion of Pyrolysis Oils On Site with Shipping to a Refinery vs IH2 Approachpp g y pp

PyrolysisOil + mild Hydroconv

i

IH2

ersion

H2 requirement at refinery 1.5‐2% none

Relative Shipping costs for oil 1 .75‐.60

ter P

hase

Pressure for hydroconversion , psi

1500‐2000 250‐500

Capital cost high medium

h

rbon

in W

a

%C in water phase 8.0 <0.2

Water cleanup issues Significant Small

Oil water separation Difficult ( easy

% C

a

emulsions likely)

% Oxygen in Product Oil


* From “Historical Developments in Bio-Oils”, Doug Elliott, Energy & Fuels 2007,21,1792-1815

Stopping halfway results in water separation issues

Novel Features of the IH2 ProcessNovel Features of the IH Process> Two stage integrated fast hydropyrolysis and

hydroconversionhydroconversion> Balanced COX and H2O production> Water Gas shift in second stage reactor to make

i it h din situ hydrogen> Self contained system with no requirements for

external H2 and methane2> Possible use of unique attrition-resistant first

stage glass ceramic catalyst As Poured Cerammed Crushed ~150μm

Reduced

C h d


Crushed(amorphous glass) (microcrystalline ceramic)

Economics for IH2

$/gal

Assumptions : Biomass $46/ton, Crude oil=$80/bbl, ROI=10%, no subsidies


Economic ComparisonFCOP +ROI $/gal

Based on 2000t/d of biomass feed

IH2


Based on 2000t/d of biomass feed

Life Cycle AnalysisLife Cycle Analysis> Preliminary LCA based on Preliminary data> Completed by Prof David Shonnard MTU Using> Completed by Prof David Shonnard – MTU – Using

Simapro database> Feed = Forest Biomass Under Natural Regenerative

Management (no application of fertilizer or pesticides)> Functional Unit is 1MJ of energy content in final fuel

content> Forest residues are collected after conventional pulp

wood and saw log harvesting> T t ti d i t k d t il> Transportation assumed a semi-truck and trailer over a

distance of 200 km


Greenhouse Gas ReductionGreenhouse Gas Reduction%

Other technologies LCA from David Hsu “Biofuels Beyond Ethanol” Sept 9 2008

IH2


Other technologies LCA from David Hsu Biofuels Beyond Ethanol Sept 9, 2008

Conclusions and Future Work

> IH2 is a promising new technology approach with excellent LCA economics potentialexcellent LCA , economics, potential

> Lots of Work to commercialize> Hydropyrolysis catalyst choice and stability> Hydropyrolysis catalyst choice and stability

> Hydropyrolysis Char – catalyst separation

> Allows feedstock providers to directly produce valuable> Allows feedstock providers to directly produce valuable hydrocarbon products

> If successfully developed, could result in significant shift success u y de e oped, cou d esu t s g ca t s tin source U.S. transportation fuel


AcknowledgementsAcknowledgements

> CRI/Criterion Inc. Catalyst was key to project success and supplied sulfided CoMo catalyst used in the hydroconversion stage of each testin the hydroconversion stage of each test

> Prof David Shonnard of MTU for LCA analysis> H2Gen for project consultation, design and costs

for integrated steam reformer


Backup slides


Lignin Structure - Cracking Points in IH 2

Carbon= 64%Perfect structure for conversion to gasoline and aromatics

Carbon= 64%Hydrogen =6%Oxygen= 30%


Cellulose Structure- Cracking Points in IH2Cellulose Structure Cracking Points in IH

nC6,nC5, CO,H2O

+ H2

IH2 makes lots of C6IH2 makes lots of C6


19/24/2009

Improvements of Biomass Physical and

Thermochemical Characteristics Via

Torrefaction Process

Samy Sadaka, Ph.D., P.E., P. Eng.Assistant Professor - Extension Engineer

Sunita NegiProgram Technician

University of Arkansas Division of AgricultureLittle Rock, AR 72204

tcbiomass2009Chicago, IL September 16-18, 2009

Introduction

Objectives

Thermochemical conversion barriers

Torrefaction

Materials and Methods

Results

Conclusion

2

Outline

3

Introduction

The proposed U.S. renewable fuels standards require

increasing the domestic supply of alternative fuels to 36

billion gallons by 2022. Out of this, 21 billion gallons

must come from advanced bio-fuels; i.e., ethanol and/or

hydrocarbon fuels from lignocellulosic biomass

(conversion of non-grain resources such as agricultural

residues, energy crops, etc.).

http://www.nrel.gov/data/pix/Jpegs/10470.jpg

Thermochemical conversion processes

barriers

49/24/2009

Although thermochemical processes have been

developed, they still have some barriers. Some of

these barriers are related to the feedstock

characteristics:

Fuel collection and transportation

Inconsistency of fuel

Fuel feeding

59/24/2009

Available technologies to improve

biomass for energy

Drying for dried solid fuel

Gasification for gaseous fuel

Pyrolysis for liquid fuels and solid by-product

Torrefaction for solid fuel

Annual production of wheat straw, rice

straw and cotton gin waste in USA.

Feedstock Million ton per year

Wheat straw 75 million ton / year

Rice straw 10 million ton / year

Cotton gin waste 7 million ton / year

69/24/2009

Source: http://www.nass.usda.gov/QuickStats/indexbysubject.jsp?Pass_group= Crops+%26+Plants:

http://www.nass.usda.gov/QuickStats/indexbysubject.jsp?Pass_group= Crops+&+Plants

http://www.nass.usda.gov/QuickStats/indexbysubject.jsp?Pass_group= Crops+&+Plants

7

Objectives

Investigate the effects of torrefaction operating

parameters on the physical and thermochemical

characteristics of wheat straw, rice straw and cotton

gin wastes.

8

Torrefaction

Torrefaction is a thermochemical pretreatment method

that is carried out by an operating temperature range of

200-300 0C in an inert atmosphere. Torrefaction is an

energy densification process that uses mild pyrolysis.

Heat (200-300 oC)

Biomass Torrefied biomass + CO + CO2 + H2O + Acids

No O2

9

Torrefaction advantages

The advantages of torrefaction process include:

Removing water uptake properties,

Eliminating biomass decompose,

Reducing grinding energy requirements and

Creating a more uniform fuel for gasification or co-

firing for electricity

Torrefied

biomass

Torrefaction

unit

Nitrogen

Raw

biomass

Gasification

Co-firing

Densification

109/24/2009

Torrefaction process

Heat

Gas

PID

controller

Data

logger

Experimental trials

Biomass Temperature

(oC)

Residence time

(min)

Wheat straw 260 0, 15, 30, 45, 60

Rice straw 260 0, 15, 30, 45, 60

Cotton gin waste 260 0, 15, 30, 45, 60

Wheat straw 200 60, 120, 180

260 60, 120, 180

315 60, 120, 180

119/24/2009

12

Effect of torrefaction time on the moisture content (%)

of wheat straw, rice straw and cotton gin waste

Time

(min)

Wheat

straw

Rice

straw

Cotton gin

wastes

0 6.69 7.17 8.29

15 4.41 4.83 7.09

30 3.90 3.63 5.10

45 3.66 3.70 4.82

60 1.98 3.63 4.26

13

Effect of torrefaction time on the volatile solids (%) of

wheat straw, rice straw and cotton gin waste

Time

(min)

Wheat

straw

Rice

straw

Cotton gin

wastes

0 82.16 71.13 82.50

15 83.15 71.13 82.49

30 83.04 69.04 82.38

45 82.49 65.25 82.23

60 80.64 64.45 81.97

14

Effect of torrefaction time on the pH of


Time

(min)

Wheat

straw

Rice

straw

Cotton gin

wastes

0 6.59 7.68 5.41

15 6.66 7.11 5.40

30 6.63 7.13 5.31

45 6.60 7.59 5.58

60 6.45 7.80 5.18

159/24/2009

Effect of torrefaction time on the heating

value of wheat straw, rice straw and cotton gin waste

169/24/2009

Effect of torrefaction time on the weight loss of


Effect of torrefaction temperature and residence

time on the moisture content of wheat straw.

Temperature

(oC)

1 Hour 2 Hours 3 Hours

25 6.69 6.69 6.69

200 0.87 0.61 0.21

260 1.98 0.34 0.00

315 0.08 0.00 0.00

179/24/2009


time on the volatile solids of wheat straw.

Temperature

(oC)


25 82.16 82.16 82.16

200 81.81 82.14 82.10

260 81.27 79.88 79.61

315 77.19 75.60 74.58

189/24/2009

Effect of torrefaction temperature and

residence time on the pH of wheat straw.

Temperature

(oC)


25 6.59 6.59 6.59

200 5.19 5.56 5.71

260 6.45 6.73 6.80

315 7.80 8.30 8.42

199/24/2009


time on the heating value of wheat straw.

Temperature

(oC)


25 16.60 16.60 16.60

200 17.03 17.56 19.40

260 19.15 19.51 22.56

315 21.73 22.28 22.75

209/24/2009


time on the mass loss of wheat straw.

Temperature

(oC)


25 0.00 0.00 0.00

200 12.34 12.16 15.80

260 23.86 33.14 33.39

315 50.34 54.14 53.86

219/24/2009


time on the fixed carbon of wheat straw.

Temperature

(oC)


25 5.46 5.47 5.46

200 8.37 10.93 11.10

260 10.48 11.15 11.69

315 12.15 11.39 13.23

229/24/2009

239/24/2009

Wheat straw as affected by

torrefaction temperature and residence time

Tim

eTemperature

249/24/2009

Torrefied wheat straw

Tim

eTemperature

25

Conclusion

Torrefaction is an exceptional technology to upgrade

biomass for combustion and gasification applications.

The torrefied biomass is superior over the raw biomass

it is produced from.

During 1 hour torrefaction at 260 oC, moisture content

was reduced by 70.5%, 49.4% and 48.6% for wheat

straw, rice straw and cotton gin waste, respectively.

The heating value increased by 15.3%, 16.9% and

6.3% for wheat straw, rice straw and cotton gin waste,

respectively during torrefaction for 1 h at 260 oC.

26

Conclusion

Increasing the torrefaction temperature above 200 oC

increased the pH values of torrefied wheat straw.

Torrefied biomass transportation cost will be reduced

due to the reduction of the biomass moisture content

and mass.

Torrefaction technology need to be introduced to the

biomass-to-energy chains.

Thank you

279/24/2009

Documents

Ctlti Hd i fBiCatalytic Hydroprocessing of Biomass Fast ... · Fast Pyrolysis Bio-oil to Produce Hydrocarbon ProductsHydrocarbon Products ... Fast pyrolysis Bio-oil Wet ----- Dry