Agricultural Bioproducts Innovation Program (ABIP)

The Agricultural BiorefineryInnovation Network (ABIN):Innovation Network (ABIN):

A Canadian Network for Research i G E F l din Green Energy, Fuels and

Chemicals

Franco BerrutiNetwork Leader

Institute for Chemicals and Fuelsfrom Alternative Resources

The University of Western OntarioLondon, Ontario, CANADA

$ 8.7 M AGRICULTURAL BIOREFINERY INNOVATION NETWORK (ABIN) [2008-2011]:

70 researchers from 17 Canadian Institutions (Academia, Government and Industry)

Vision of ABIN

• to enable Canada to exploit its plentiful supplies of biomass, pp ,

• focusing on agricultural (non-food) co-products, residues, and selected energy crops

• through research and development of novel technologies for the economical and tec o og es o t e eco o ca a dsustainable conversion of such resources into energy and value-added products,

d t t th d l t f th• and to support the development of the emerging bio-based economy

Goal of ABINContribute to, and encourage,

t i bl d l tsustainable development while strengthening Canada’s rural economy with the creation of new businesses and jobs

Key Features of Vision (1)

• Similarly to the developments of the past century using petroleum feedstocks, we are focusing on the BIOREFINERY approach, where the feedstock is a sustainable, renewable, and low value material and a large spectrum of value-added products are generated in

Key Features of Vision (2)

• The key elements are:The key elements are:• full life-cycle assessment,

sustainability• sustainability, • environmental preservation• creation of value and jobs.

Key Features of Vision (3)C ti l t f ti• Connecting clusters of expertise from across Canada and leveraging

isynergies, • Sharing and distribution of

k l d l t d t thknowledge related to the advancement of biorefining, C t ib ti t th d l t f• Contribution to the development of a vigorous and enduring Canadian bi th h d ti dbioeconomy through education and training of HQP

Participating InstitutionsUniversity of Western Ontario University of Toronto

École Polytechnique de Montreal University of Northern British Col mbiaColumbia

University of Guelph University of AlbertaUniversity of Manitoba Agri-Therm LimitedRyerson University Perth Community FuturesUniversity of Saskatchewan Saskatchewan Research Council

Université de Sherbrooke Stormfisher LtdUniversité de Sherbrooke Stormfisher Ltd.University of British Columbia National Research Council

Agriculture and Agri-Food CanadaCanada

Research Themes:

1. Feedstock Enhancements and Biorefinery Interface

2. Green Chemicals3. Green Fuels4. Green Energy5. Life-Cycle Assessment and Technology

IntegrationIntegration6. Knowledge Transfer, Technology Transfer,

Commercialization and Policy Development

1) Feedstock Enhancement and )Biorefinery Interface L. Tabil (UofS), S. Sokhansanj (UBC), S. Panigrahi (UofS), G. Turcotte (Ryerson), P. ( ) j ( ) g ( ) ( y )Krishna (Western), R. Knox (AAFC), N. Huner (Western)

• Research to reduce handling, storage and g gprocessing costs, and to ensure a steady supply of agricultural-based lingocellulosic feedstocks required for biorefineriesfor biorefineries

PROJECTS:

• Pre-processing and densificationp g• Rheology of pre-processed straw• Feedstock genetic optimization• Feedstock genetic optimization• Supercritical CO2 pre-treatment prior to

h d l ienzyme hydrolysis

2) Green ChemicalsC. Briens (Western), I. Scott (AAFC), F. Berruti (Western), X. Bi (UBC), J. Chaouki (École Poly), P. Charpentier (Western), E. Chornet (Sherbrooke), A. Dalai (UofS), Y. Dahman (Ryerson), R. Dutton (Guelph), R. Golden (Agri-Therm), B. McGarvey (AAFC), S. Liss (Gueph)(Gueph)

• Research on the efficient use of crops or plant residual materials to generate valuable chemicals and pharmaceuticals for agricultural, industrial or medicinal uses (i.e., green chemicals)medicinal uses (i.e., green chemicals)

PROJECTS:

• Pyrolytic bio-oil production • Reactor Technology: fluid bed rotating fluid bedReactor Technology: fluid bed, rotating fluid bed,

microwave• Chemical identification and biological activity of bio-g y

oils• Extraction and separation• Glycerol conversion• Bio-char• Monomers and polymers• Functional biomaterials

3) Green FuelsA. Dalai (UofS), J. Chaouki (École Poly), R. Ranganathan (SRC), D. Anweiler (SRC), N. Ellis (UBC), K. Smith (UBC), S. Duff (UBC), P Watkinson (UBC), N. Abatzoglou (Sherbrooke), E. Chornet (Sherbrooke), C. Briens (Western), F. Berruti (Western), H. DeLasa (Western), H. Wang (NRC), G. Wolfaardt (Ryerson), Y. Dahman (Ryerson), A. Lohi (Ryerson) G Hill (UofS) J Kozinski (UofS) T ugsley (UofS) C Niu (UofS) BLohi (Ryerson), G. Hill (UofS), J. Kozinski (UofS), T. ugsley (UofS), C. Niu (UofS), B. Roesler (PhibrioChem), D. Bayrock (PhibrioChem), S. Helle (UNBC), W. McCaffrey (UofA), M. Thomson (UofT)

D l i t t d d i i l h f th• Develop integrated and original approaches for the complete utilization of biomass feedstocks to produce green fuel productsp g p

PROJECTS:

• Bio-diesel production and application p pp(nanocatalysts, quality improvement)

• Bio-oil production and upgradingBio oil production and upgrading• Syn-gas, Hydrogen and Bio-gas

Bi th l d bi b t l• Bio-ethanol and bio-butanol

4) Green Energy

M. Thomson (UofT), A. Dalai (UofS), J. Chaouki (École Poly), C. Briens (Western), F. Berruti (Western), H. Wang (NRC), G. Hill (UofS), E. Bibeau (Manitoba) ( ) g ( ) ( ) ( )

• Integrates fuel cells, pyrolysis, combustion and biological technologies for heat and powerbiological technologies for heat and power production into sustainable agricultural cycles. Research related to production of green energy.

PROJECTS:

• Pyrolysis bio-oil for heat and powerC b ti f bi i t d b d• Combustion of biomass in spouted bed

• Direct Liquid Fuel Cells for bio-fuels• Algae growth in CO2 for ethanol and

electricityy• Brayton Hybrid Cycle for heat and power

5) Life Assessment and Technology Integration

L. Townley-Smith (AAFC), R. Samson (École Poly), L. Deschenes (École Poly), X. Bi (UBC), M. Wismer (SRC)

g

• Life cycle approach:• integrate the environmental variablesintegrate the environmental variables• optimize industrial processes• minimize the risk of major problems after the

introduction of one of these technologies and ensure that the new technology does not shift the problem elsewherethe problem elsewhere

PROJECTS:

• Biomass inventory mapping and analysis y pp g ytools integration in LCA

• LC inventory database for biofuel andLC inventory database for biofuel and bioenergy

• Energy and materials flows in biofuels• Energy and materials flows in biofuels production

6) Knowledge Transfer, Technology Transfer, Commercialization and Policy DevelopmentCommercialization and Policy Development

T. Bansal (Western), D. Cunningham (Western), C. Guilon (StormFisher), B. van Berkel (StormFisher), R. Golden (Agri-Therm), J. Henhoeffer (PCFDC), D. Lee (AAFC), L . Townley-Smith (AAFC), M. Stumborg (AAFC), J. Adams (Western), D. Hewson (Western), J. Kabel ( ) g ( ) ( ) ( )(Western), R. Ranganathan (SRC)

• Investigate existing knowledge networks to identify the g g g ykey success factors required to develop sustainable biorefinery clusters in Canada

• Examine the degree political (policy) economic and• Examine the degree political (policy), economic and social factors will influence entrepreneurial firms’ technology development decision-making and performance.

PROJECTS:

• Existing knowledge and success factors to g gdevelop sustainable biorefinery clusters

• Influence of political economic and socialInfluence of political, economic and social factors on entrepreneurial firms’ technology decision-making andtechnology, decision making and performance

ABIN Administration• Network LeadNetwork Lead

Franco Berruti berruti@eng.uwo.ca

• Network Manager Chantal Gloor cgloor@eng.uwo.ca

• Financial Administrative AssistantPi S b b @Pina Sorbara psorbara@eng.uwo.ca

• Administrative Assistant• Administrative AssistantChristine Ramsden cramsden@eng.uwo.ca

ABIN Governance• Network Management Committee chairedNetwork Management Committee, chaired

successively by a Federal Network Lead and the Recipient Network Lead, with membership

t ti f ll 6 th t t l t 2representation from all 6 themes; meet at least 2 times annually

• Board of Directors with a role to recommend strategies to heighten the relevance and impact f th k l ll id tif iof the work plans, as well as identifying

mechanisms related top sustainability of Network.

MATHEMATICAL FORMULATION (Eulerian-Eulerian Method)

Continuity equations for gas and solid are as follows;

,

Momentum equations for gas and solid are as follows;

Energy equations for gas and solid are as follows;

Species equations for gas and solid are as follows;

,

COMPUTATIONAL CONDITIONS

RESULTS AND DISCUSSION

CONCLUDING REMARKS

In the present study, CFD is applied to the gas-particle flows with pyrolysis reaction in the gravity-driven reactor. To analyze the pyrolysis reaction of the reactor, the

semi-global two stage chemical kinetics having tar cracking mechanism is applied. From the results, it is noted that the vigorous motions of the hot sand particles

with higher granular temperature may be helpful to mixing between wood and sand particles and the consequent heat transfer for fast pyrolysis from sand to wood.

Numerical Study of Fast Pyrolysis of Woody Biomass in a Gravity-

Driven Reactor

1. Environment and Energy Systems Research Division, Korea Institute of Machinery Materials, Daejeon, South Korea

* Corresponding author: hschoi@kimm.re.kr

INTRODUCTION

To overcome environmental problems such as CO2 discharge caused by fossil fuels, fast pyrolysis method becomes bright prospect for

thermal conversion of biomass into biocrude-oil, which can be used for heat and power generation and additionally bio-refinery.

In order to design cost-effective fast pyrolysis reactor, it is necessary to increase biocrude-oil yield and, at the same time, to decrease

energy and working materials which are needed for the fast pyrolysis process.

Hence, simple gravity-driven reactor is devised in the present study, which does not demand working fluids and related energy to run

them typically needed for fluidizing techniques.

In the present study, the gravity-driven fast pyrolysis reactor is simplified as an inclined 2-dimensional duct and the flow and thermal

fields of the reactor and furthermore the effects of inclined angle and inlet height for sand are numerically investigated as a starting point

for the optimal design of the reactor and for future industrial application.

H.S. Choi1*, Y.S. Choi1, S.J. Kim1

Computational Conditions

Fig.1.(a) Gas velocity vector

Computational Domain

In Fig.1 (a), weak flow-recirculation region appears

upstream near the inlets and toward downstream the gas

flow is developed following the solid flow. For the

primary reaction rate of tar production (R1), the reaction

mainly takes place at very close to the bottom wall and

tar mass fraction is increased downstream. The mass

fraction of non-condensable gas and char density are

increased toward downstream in Figs.1 (d) and (e). In

particular, from Fig.1 (c) and Fig.2 (c), the tar entrained

into the flow recirculation region becomes non-

condensable gas by the secondary reaction. Hence, the

length of reactor and the recirculation region should be

carefully considered to reduce the secondary reaction.

In Fig.3, it is noted that the maximum primary reaction

rates are located between the first and second peaks of

the granular temperature at very close to the wall, where

wood particles are heated by hot sand as well as the

heated bottom wall. Although, in general, the magnitude

of granular temperature is known as small compared

with mean particle velocity, the vigorous motions of the

hot sand and wood particles with higher granular

temperature may be helpful to mixing between wood and

sand particles and the consequent heat transfer from

sand to wood. In Fig.4, the case2 shows the highest

values of R1 and R4 compared with others at four

different streamwise positions. It is noted that in Fig.4 (a)

case2 has the highest R1 value and case 1 has the lowest

one, where the peak magnitude of granular temperature

shows the same pattern. Hence, the solid mixing and

consequent heat transfer have a great effect on the fast

pyrolysis reaction.

Gravity-Driven Reactor

for Fast Pyrolysis

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Computational Domain (2- Dimensional)

Length (L) 100 cm

Height (H) 10 cm

Grid allocation (x,y) 100 x 35

Boundary Conditions

Sand inlet Dirichlet (Vinlet=7.37 cm/s, T inlet=753 K)

Woody biomass inlet Dirichlet (Vinlet=7.37 cm/s, Tinlet=300 K)

Outlet Neumann

Wall Johnson and Jackson, Dirichlet(T wall=753 K)

Particle Density

Wood 0.65 g/cm3

Char 1.0 g/cm3

Sand 2.5 g/cm3

Validation for Inclined Chute Flow

Semi-global Two Stage Reaction Mechanism for

Wood Pyrolysis

Fig.1.(b) The primary reaction rate for tar (R1) Fig.1.(c) Mass fraction of tar by primary reaction

Fig.1.(d) Mass fraction of non-condensable gas by primary reaction Fig.1.(e) Density of char by primary reaction

Fig.2.(a) The secondary reaction rate for non-condensable gas (R4) Fig.2.(b) The secondary reaction rate for char (R5)

Fig.2.(d) Density of char by secondary reactionFig.2.(c) Mass fraction of non-condensable gas by secondary reaction

Fig.3.(a) Reaction rates at x/H=3, (b) Granular temperature for sand at x/H=3, (c) Reaction rates for R1, (d) Granular temperatures for sand

Fig.4. Reaction rate R1; (a) x/H=1, (b) x/H=3, (c) x/H=9, Reaction rate R4; (d) x/H=1, (e) x/H=3, (f) x/H=9

(Case1: inclination angle of 45◦, Case2: inlet height for sand is increased to 4 times larger than that of case1, Case3: inclination angle of 55◦)

(d)

(b) (c) (d)

(a) (b) (c)

(a)

(e) (f)

A cooperative program by:Amber Broch, S. Kent Hoekman

PROCESS OPTIMIZATION DRI is collecting and analyzing all products of the HPT process from a variety of feedstocks (loblolly pine, rice hulls, corn stover, pinion/ juniper chips, and white fir/Jeffery pine chips. The products include:

To demonstrate the viability of the pre-treatment process, we intend to use the bio-char as feedstock for a gasifier. DRI is partnering with UNR’s College of Agriculture, which has acquired a Biomax 15, a commercial gasifier/ power generation system.

BIOMAX 15The Biomax 15, manu- factured by Community Power Corp. (CPC), produces syngas by gasification of wood chips. The syngas is then combusted in an engine/ generator set to

The Biomax 15 produces 15 kW of electrical power by burning syngas from gasification of biomass in a generator.

produce 15 kW of electrical power and provide available heat. We intend to run the Biomax using pre-treated, Nevada-specific biomass.

SYNGAS CHARACTERIZATIONDilution sampling will be used to collect syngas from:

• raw wood feedstock• HPT wood feedstock• conventionally torrefied

wood feedstock

This work was performed under a subcontract to the Gas Technology Institute to support the technical goals of US DOE Cooperative Agreement DE-FG36-01GO11082DRI Participants : Jay Arnone, Amber Broch, Alan Gertler, Kent Hoekman, Richard Jasoni, Steve Kohl, Tim Minor, Jeremy Riggle, Curt Robbins, Lycia Ronchetti, Vera Samburova, Dave Sodeman, Paul Verburg, Barbara Zielinska.UNR Participants: Chuck Coronella, Victor Vasquez, Wei YanREII Participants: Matt Caldwell, Dennis Schuetzle, Greg Tamblyn

A techno-economic analysis of the pre-treatment process is being conducted to determine the viability of building a full-scale, commercial facility in Nevada.

• This analysis incorporates results of the resource assessment and the mass/energy balances of the pre-treatment process.

• Hydrothermal pre-treatment will be coupled with gasification (for syngas production) or pyrolysis (for bio-oil production).

• Based upon results of the Nevada biomass resource assessment, the facility would be located in Eastern Nevada.

Canister SamplerCarbonyl

Sampler

Tenax (VOC) Sampler

Dilution Tunnel

Canister SamplerCarbonyl

Sampler

Tenax (VOC) Sampler

Canister SamplerCarbonyl

Sampler

Tenax (VOC) Sampler

Dilution Tunnel

Equipment for sampling and analysis of syngas.

• Pre-treated solid biomass or “bio-char”• Condensed liquid• Gases

Through a comprehensive set of lab analyses, we will perform complete mass and energy balances of the HPT process. This includes ultimate and proximate analyses, lignocellulosic composition, and detailed chemical analysis.

PRELIMINARY DATA AND RESULTS

Some preliminary results from HPT of Alabama Loblolly Pine are shown in Figures 3 & 4 below. The mass of the recovered dry bio- char is calculated through moisture measurements. In this case, the recovered solid is lower than expected, due to uncertainties in the moisture content of the recovered wet bio-char.

Feedstock Biochar Feedstock Biochar Feedstock BiocharC 51.4 68.3 43.1 48.7 39 43.2H 5.9 5.1 5.3 4.7 4.8 4N 0.23 0.37 0.75 0.94 0.26 0.4S 0.04 0.03 0.09 0.1 0.06 0.05O 42.1 25.9 40.1 30.7 35.6 24

Ash 0.39 0.27 10.9 14.7 20.4 27.9Dry HV (Btu/lb) 8511 11793 7207 8239 6650 7328

Loblolly Pine Corn Stover Rice HullsUltimate Analysis %

Ultimate analyses of three different raw feedstocks and resulting biochar produced by the HPT process are summarized below. Note the increase in energy content and C, and the decrease in O.

To support a DOE Cooperative Agreement with the Gas Technology Institute (GTI), DRI is partnering with the University of Nevada, Reno (UNR), the Renewable Energy Institute International (REII), and Changing World Technologies (CWT) to demonstrate the viability of hydrothermal pre-treatment as a method to convert lignocellulosic biomass into a uniform, densified feedstock that could be easily fed into a thermo-chemical conversion process to produce syngas, pyrolysis oils, and other value-added products. DRI is focused on feedstocks available in the State of Nevada, and is also conducting a biomass resource assessment within the State.

Biomass feedstocks include a wide variety of materials that exhibit significant differences in handling characteristics, energy content, and recalcitrance to conversion -- all factors that must be accommodated within a biorefinery context. Hydrothermal pretreatment of biomass promises to produce a uniform solid that can be easily fed to any thermochemical conversion process.

HYDROTHERMAL PRETREATMENT (HPT)

Technical Accomplishments

• The O content is lowered, but C content is increased.

• The process takes less time than conventional dry- torrefaction.

• The mass of the feedstock decreases while its energy content is mostly retained.

Figure 1. Loblolly pine chips before and after pre-treatment

Figure 2. HPT lowers O content and increases C content, making biomass more similar to coal.

0.40 0.2 0.80.6

0.2

0.4

1.0

1.2

1.4

1.8

0.8

0.6

1.6

Atomic O/C ratio

Ato

mic

H/C

ratio

Biomass

Peat

LigniteCoal

Anthracite

Increased Heating Value

WoodLigninCellulosePretreated Wood

Pretreated Corn Stover and Rice Hulls

Torrefied Wood

Raw Corn Stover and Rice Hulls

0.40 0.2 0.80.6

0.2

0.4

1.0

1.2

1.4

1.8

0.8

0.6

1.6

Atomic O/C ratio

Ato

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H/C

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Biomass

Peat

LigniteCoal

Anthracite

Increased Heating Value

WoodLigninCellulosePretreated Wood

Pretreated Corn Stover and Rice Hulls

Torrefied Wood

Raw Corn Stover and Rice Hulls

WoodLigninCellulosePretreated Wood

Pretreated Corn Stover and Rice Hulls

Torrefied Wood

Raw Corn Stover and Rice Hulls

HPT transforms lignocellulosic biomass into a uniform, friable solid with much higher mass and energy densities than the parent biomass (Fig. 2)

ApproachBiomass is treated in water at temperatures around 260°C and equilibrium pressures (~680 psig) for 2- 5 minutes to produce a hydrophobic solid that is easily dried and pelletized. Other products include non- condensable gases and condensed liquid that is mostly water (Fig. 3)

Figure 3. Total material recovery from HPT of Alabama Loblolly Pine. 95% of starting material is recovered. About 54% of the dry starting material is accounted for. (Based on moisture content measurement of 78.2% for the wet bio-char)

Figure 4: Chemical analysis of products from HPT processing of Loblolly Pine. 100% of the gaseous product is identified; 34% of dry bio-char is identified; <1% of the condensed liquid is identified.

20 g Gas 619g Condensed Liquid 5.6 g dissolved solid 312 g Wet Biochar 39g dry Biochar (13 g identified)

Unidentified (assumed H2O)

(99.07%)Dissolved

Solids0.93%

Polars (0.17%)Cations &

Anions (0.02%)

Other Elements (0.01%)

Acetic Acid (0.31%)

Other Organic Acids

(0.09 %)

Unidentified organics ( 0.34%)

Other Organic Acids

(0.8%)

Elements (0.8%)

Furans (17.3%)

Dry BiocharIdentified *

Hydroxy Acids (4.1%)

Other Polars (7.2%)

Acetic Acid (1.3%)

LigninMonomers

(0.5%)

Monosaccharides (2.2%)

Moisture in Biochar 78.2%

Dry Bio-Char

Unidentified

Percentages based on dry biochar: 34.2% identif ied

CO(4%)

Other(2%)

CO2 (94%)

20 g Gas 619g Condensed Liquid 5.6 g dissolved solid 312 g Wet Biochar 39g dry Biochar (13 g identified)

Unidentified (assumed H2O)

(99.07%)Dissolved

Solids0.93%

Polars (0.17%)Cations &

Anions (0.02%)

Other Elements (0.01%)

Acetic Acid (0.31%)

Other Organic Acids

(0.09 %)

Unidentified organics ( 0.34%)

Other Organic Acids

(0.8%)

Elements (0.8%)

Furans (17.3%)

Dry BiocharIdentified *

Hydroxy Acids (4.1%)

Other Polars (7.2%)

Acetic Acid (1.3%)

LigninMonomers

(0.5%)

Monosaccharides (2.2%)

Moisture in Biochar 78.2%

Dry Bio-Char

Unidentified

Percentages based on dry biochar: 34.2% identif ied

CO(4%)

Other(2%)

CO2 (94%)

CO(4%)

Other(2%)

CO2 (94%)

*

Thermogravimetric analysis and devolatilization of wood under nitrogen and steam gas atmospheres.Igor V. Kolomitsyn, Andriy B. Khotkevych, Donald R. Fosnacht.

Natural Resources Research Institute, University of Minnesota Duluth, Minnesota. 5013 Miller Trunk Hwy., Duluth, MN, 55811.

Abstract.

Thermogravimetric plots have been measured in range from 393 K to 1023 K for several hard woods (yellow poplar,

aspen) and soft woods (red pine and spruce) under nitrogen gas atmosphere on a 50 g scale. The typical ramping speed

was (2 – 5) K/min. Temperatures for thermal events for each species were recorded. A comparison between hard

woods and soft woods shows that, in the latter case, the decomposition starts at lower temperature. A tubular fixed bed

reactor was used to investigate each thermal event under nitrogen and steam gas atmospheres at the constant

temperature settings. Each sample before thermal treatment was dried at 373 K for 24 hrs. Volatiles and wood

extractives before and after thermal treatment were analyzed using gas chromatography mass spectroscopy (GC/MS)

technique. It was found that at 503 K – 543 K under steam gas atmosphere, extractible phenols, fatty alcohols, and

fatty acids were accumulated in the volatile fraction. The solid residue after thermal treatment was also analyzed. The

concentration of D(+)-xylose, D(+)-mannose, L(+)-arabinose, D(+)-glucose, D(+)-galactose in each sample before and

after thermal treatment at various temperatures was measured by high performance liquid chromatography (HPLC)

technique. These data are used to estimate the concentration of cellulose and hemicellulose in wood samples. The

purpose of this investigation is to develop a lignocellulosic pre-treatment regime that allows more easy access of the

cellulosic sugars for conversion of the materials to liquid fuel by either bio or thermal conversion methods.

References

1. Amidon, T. E.; Liu, S., Water-based woody biorefinery. Biotechnology Advances 2009, 27, (5), 542-550.

2. Fieser, L. F.; Fieser, M. Diazomethane. In: Reagents for Organic Synthesis. New-York, John Wiley & Sons, Inc, 1967, p. 191.

3. Supelco. Guide to Derivatization Reagents for GC. Bulletin 909.

4. Standard Test Method for Determination of Carbohydrates in Biomass by High Performance Liquid Chromatography. ASTM

International, E 1758-01. 2007.

Results and Discussion.

Conclusions

The decomposition of softwood starts at lower temperature (about 260 oC) compared to the decomposition temperature of

hardwood;

The thermochemical reaction of softwood started by the decomposition of the arabinoglucoroxylan in the hemicelluloses.

Extractibles of spruce wood are separated in the steam atmosphere. Phenols, aromatic aldehydes, fatty acids, fatty alcohols

and non-polar rosins are found in a volatile fraction whereas rosin acids stay in the wood.

Rosin acids started to decompose in N2 and steam atmosphere at 260 oC.

TC

N2 Fixed Bed Tube Reactor:

The 12” long ½” ID reaction tube is connected to the gas/steam supply on the top, and to the

charcoal trap on a bottom. The sample of wood chips is being loaded as shown, over the glass fiber

plug. The process runs at manually adjusted flow rate and at PID-controlled outside tube

temperature. The inside temperature has been recorded with a separate device. The work pressure

has been kept within (6 – 8) psig – as low as needed to maintain selected flow rate.

After the exposure time is over, the tube has been placed out of the heater, allowing it to cool down

at ~20 C/min, and then the sample has been unloaded, weighed and analyzed.

The charcoal from the trap, alongside with the fiber plug have been and extracted in Soxlett with

dichloromethane to determine the amount and composition of the volatile matter.

The Upscale Thermogravimetric Apparatus (TGA):

The specially designed unit allows to get thermogravimetric plots on the relatively large samples of

material (30 – 50 grams, in case of wood chips).

The sample of wood chips is being loaded as shown, in the Inconel cup, placed on a tip of a long-

shaft thermocouple. The weight of assembly is being monitored live with 0.02 g accuracy. The

process is typically running at manually adjusted flow rate and at PID-controlled outside wall

temperature. The inside temperature has been monitored separately, using the wireless transmitter

on the top of the thermocouple assembly.

The TGA-tests have been made in nitrogen atmosphere at constant ramping speed within (2.5 – 3.5)

C/min.

Gas chromatography-mass spectroscopy (GC/MS) method:

GC/MS analysis was performed using a Hewlett Packard Gas Chromatograph Model 5890, which was equipped with Hewlett

Packard Mass Selective Detector 5970A, and capillary column (Optima-1 12 m x 0.2 mm with film thickness 0.2 mm;

Macherey-Nagel Inc., Cat # 726834.12. ). The program conditions that were used are as follows: column was kept 1 min at

80oC and then heated from 80 oC to 250 oC with a heating rate of 10oC/min, then kept at 250 oC for 10 min. Injector

temperature was held at 300 oC and detector temperature was held at 300oC. Solvent delay: 5 min. Head pressure was 7 psi.

Carrier gas: He. Injection volume: 1 ml. All samples before injection were methylated using a solution of CH2N2 in ether [2]

and then silylated with BSTFA [3].

HPLC chromatographic conditions:

The analysis was performed on a Shimadzu (Shimadzu Scientific Instruments, Inc., Columbia, MD, U.S.A.) liquid

chromatographic system consisting of a Model SCL-10Avp system controller, a Model DGU-14A on-line Degasser, a Model

LC-10ATvp HPLC pump, a Model FCV-10ALvp Low-pressure Gradient Flow Control Valve, a Model SIL – 20A auto

sampler, a Model RID-20A refractive index detector, and a Model CTO-20A column oven. For data acquisition and analysis

the Shimadzu EZStart Ver. 7.2.SP1 was used. The chromatographic column utilized was VA 300/7.8 Nucleogel Sugar Pd2+,

(Macherey-Nagel Inc., Cat # 719530.) Elution was carried out in the isocratic mode at a flow-rate of 0.4 mL/min. HPLC grade

water was used a suitable mobile phase. Elution time was 30 min; column temperature was 80 oC, and injection volume was 50

μL.

HPLC analysis of cellulose and hemicelluloses:

Carbohydrate analysis by HPLC was performed by modified procedure from ASTM 1758-01 [4]. Stock solution (5.1 mg/mL)

of reference compounds (glucose, xylose, galactose, mannose, and arabinose) was prepared in water (HPLC grade). Dilutions

were obtained in water to afford the concentration range 0.4 mg/mL to 5.1 mg/mL. The standard solution was injected in

triplicate and the curve was constructed using the average values of the detector response. Calibration curve was as follow (X –

peak area; Y – concentration of monosaccharide (mg/ml)):

Glucose Y = 9.13E(-7)*X + 0.026891794 R2 = 0.999

Xylose Y = 9.9E(-7)*X + 0.03504039 R2 = 0.999

Galactose Y = 1.690E(-6)*X - 0.048736458 R2 = 0.999

Mannose Y = 9.56E(-7)*X + 0.065521422 R2 = 0.999

Arabinose Y = 1.017E(-6)*X + 0.032770391 R2 = 0.999

For quantitative analysis, the samples of temperature treated wood were hydrolysed ucording to the procedure [4] and after

chromatographic separation the amount of glucose, xylose, galactose, mannose, arabinose were calculated from the calibration

curve.

TC

1. Solid and volatile matter at variable process temperature.

Softwood (Red Pine) Hardwood (Yellow Poplar)

0

2

4

6

8

10

12

14

16

18

20

290 300 310 320 330 340 350 360 370 380 390

Condensable matter, % (Tube)

°C

20

30

40

50

60

70

80

90

100

200 250 300 350 400 450 500

Solid matter, %

Tube

TGA

°C

Surprisingly, both hardwood and softwood samples in the tube reactor (10 min.,

N2, GHSV = 200) show much more weight loss, compared to the same in TGA

arrangement. This difference is more evident at temperatures below 350 °C. At

higher temperatures the weight plots are going to be similar, no matter what

arrangement is employed.

The yield of condensable volatile products shows some complex temperature

dependence with a local hump at (340 – 350) °C. At this point, the pyrolysis

reactions begin to dominate in the overall process. This can also confirmed by

comparison of the composition of products.

2. Effect of Gas Flow Rate.

In case of softwood, the process of devolatilization shows major dependence on a

gas flow rate. Probably, the volatile components of a softwood have a trend to re-

condensation or recombination at a solid matrix. Increase of the flow rate

(dilution of the gas media with inert carrier gas) makes this process slow down.

For hardwood, the changes of flow rate are effective below GHSV = 50, and

almost no effect has been observed at higher values.

60

65

70

75

80

85

90

95

100

0 50 100 150 200 250 300 350

Softwood (South Yellow Pine)

Hardwood (Yellow Poplar)

Solid matter, %

N2, GHSV*

Setup: Fixed Bed Tube

Process Temperature: 300°C

Process Time: 10 min.

* The “Zero GHSV” points were obtained in the TGA arrangement.

3. Effect of the Process Time.

55

60

65

70

75

80

85

10 15 20 25 30min.min.

Softwood (South Yellow Pine)

Hardwood (Yellow Poplar)

55

60

65

70

75

80

85

10 15 20 25 30

Solid matter, % : T = 305 C Same, 325 C

Setup: Fixed Bed Tube

Carrier Gas: N2

GHSV = 200

Unlike the case above, the process time effects more on devolatilization of

hardwood, then softwood. The effect of the process time is more evident at lower

temperatures, when pyrolitic processes possess the minor role in overall reaction.

At higher temperatures, when pyrolysis becomes the dominate reaction, the effect of

process time becomes insignificant.

In the typical process conditions the temperature inside of the

sample cup lags within (5 - 7) °C behind the oven. However,

the spontaneous temperature rise takes place when the sample

goes from 300 to 400 °C. The peak on the plot is about 15 °C

high, and is matching the temperature, when decomposition of

the sample is most extensive (see TGA plots at 1.) This effect

confirms the exothermic nature of some reactions, which take

place during pyrolysis of wood biomass.

4. Autothermal effects.

200

250

300

350

400

450

500

200 300 400 500

Softwood (Tamarack)

Hardwood (Aspen)

Oven, C

Sample, C

-8

-6

-4

-2

0

2

4

6

8

10

12

200 250 300 350 400 450 500

Rise, C

Oven, C

Setup: Upscale TGA

Load of material: 35 – 45 g

Ramping speed: 3.3 C/min.

Introduction.

The purpose of this investigation is to develop a pretreatment regimes for various lignocellulosic materials, that allows

more easy access to the individual cellulosic carbohydrates. This carbohydrates may be further converted to liquid fuels

by either bio or thermal conversion methods.

Chemicals Percentage by weight, %

Hemicelluloses Softwood Hardwood

25-30 15-35

Galactoglucomannan (1:1:3) 5-8 0

Galactoglucomannan (0.1:1:4) 10-15 0

Glucomannan (1:2 – 1:4) 0 2-5

Arabinoglucoroxylan 7-10 Trace

Glucoronoxylan Trace 15-30

Cellulose ( ) 40-44 40-44

Lignin 25-35 18-25

Extractives 5-8 2-8

Table 1. Major component of wood. [1]

Experimental.

The experiments on devolatilization of various wood samples have been conducted in a stainless steel Fixed Bed tube

reactor. For comparison, some samples have been treated via TGA-like procedure in the specially designed unit. The

products of devolatilization have been maintained using conventional wet lab techniques.

Materials:

All commercial reagents were ACS reagent grade and used without further purification..

5. Composition of solid residues of softwood at variable process temperature.

Minutes

16 18 20 22 24 26 28 30

uR

IU

0

10

20

uR

IU

0

10

20

19.8

50

21.3

67

23.1

92

24.9

42

26.4

08

RID10A ivk2809s2 r1 spruce 230C 06-01-2009 06-23-21 PM-Rep2.dat

Retention Time

Spruce T=230oC

Minutes

16 18 20 22 24 26 28 30

uR

IU

0

10

20

uR

IU

0

10

20

19.8

50

21.3

67

23.1

92

24.9

42

26.4

08

RID10A ivk2809s3 r1 spruce 245C 06-01-2009 07-57-15 PM-Rep2.dat

Retention TimeSpruce T=245

oC

Minutes

16 18 20 22 24 26 28 30

uR

IU

0

10

20

uR

IU

0

10

20

19.8

50 2

1.3

67

23.1

92

26.3

75

RID10A ivk2809s4 r1 spruce 260C 06-01-2009 10-02-30 PM-Rep3.dat

Retention Time

Spruce T=260oC

Minutes

16 18 20 22 24 26 28 30

uR

IU

0

10

20

uR

IU

0

10

20

19.8

58

21.3

75

23.2

00

24.9

50

26.4

08

RID10A ivk2809s1 r1 spruce wood 06-01-2009 04-49-27 PM-Rep2.dat

Retention Time

Softwood profile (Spruce)Glucose

Xylose

Galactose

Arabinose

Mannose

Chromatograms of solid residue of

thermally treated softwood.

Thermochemical reaction of

softwood (White Spruce) started by

hemicelluloses decomposition at 260oC. In the fixed bed tube reactor the

concentration of arabinose is

decreased to an undetectable level.

This data strongly support the idea

that thermochemical reaction of

hemicelluloses occurred by the

arabinoglucoroxylan decomposition.

6.00 8.00 10.00 12.00 14.00 16.000

500000

1000000

1500000

2000000

Time-->

AbundanceTIC: I1509S4A.D

5.676.24 7.387.497.93

8.67

8.98 9.8310.03 12.08

13.30

13.47

13.66

14.1114.83

15.07

15.46

15.56

15.77

16.19

16.64

17.0017.7418.31

6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00

200000

400000

600000

800000

1000000

1200000

1400000

1600000

1800000

2000000

2200000

Time-->

AbundanceTIC: 2209S2B.D

8.65

15.05

15.40

15.64

15.73

16.13

16.39

16.51

17.70

6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00

200000

300000

400000

500000

600000

700000

800000

900000

1000000

1100000

Time-->

AbundanceTIC: 2209S4A.D

5.66

6.50

6.76

7.38

8.639.43

9.69

10.19

10.38

12.05

12.7713.03

13.25

13.43

13.62

13.71

14.25

15.00

15.3815.69

16.9417.38

6. GC/MS profile of extractibles of softwood .

Extract of spruce wood.Extract of spruce wood after treatment at 230

oC.

Volatiles of spruce wood after treatment at 230 oC.

RT, min Name

15.40Rosin acids

15.73

16.13 Abietic acid Abietic acid

Phenols, methoxybenzols,

aromatic aldehydes

C18:0

C18:2

Rosins

INTEGRATED HEAT, ELECTRICITY AND BIO-OIL PRODUCTION

J. Lehtoa,*, P. Jokelab, Y. Solantaustac, A. Oasmaac

aMetso Power, Kelloportinkatu 1 D, PO Box 109, FI-33101 Tampere, FinlandbUPM, Eteläesplanadi 2, PO Box 380, FI-00101 Helsinki, Finland

cVTT, Biologinkuja 5, PO Box 1000, FI-02044 VTT, Finland*Corresponding author. Tel: + 358 20 14121 Fax: + 358 20 1412 210

E-mail: jani.lehto@metso.com

INTEGRATION REDUCES THE COSTS

A fast pyrolysis unit can be integrated with a fluidized bed boiler. Based on such a concept, the pyrolysis unit utilizes the hot sand in the fluidized bed boiler as a heat source. The devolatilized gas compounds are condensed into bio oil and the remaining solids, including sand and fuel char, returned to the fluidized bed boiler. In the boiler, the remaining fuel char and non-condensable gases are combusted to produce heat and electricity.

ON-LINE QUALITY CONTROL IN USE

Quality follow-up along the entire chain from biomass processing via pyrolysis to oil use, will both ensure the production of a consistently high-quality product and help in avoiding possible problems during production. Standard and novel on-line methods will be used and further developed.

FIELD TESTS FOR VERIFICATION THE BOILER CONCEPT

UPM’s focus is on using bio-oil as a substitute for light and heavy fuel oil in heating and combined heat and power plants. Oilon is currently developing a new burner for pyrolysis oils, to be tested in Finland in 2009.

A 2 MW fuel fast pyrolysis unit has been integrated with Metso’s 4 MWthcirculating fluidized bed boiler, located at Metso’s R&D Center in Tampere

WORLD’S FIRST INTEGRATED PYROLYSIS PLANT

Metso has built the world’s first integrated pyrolysis pilot plant in Finland, in co-operation with UPM and VTT. The related concept covers the entire business chain, from feedstock purchase and pre-treatment to bio-oil production, transportation, storage and end use. This project is partly funded by TEKES, the Finnish Funding Agency for Technology and Innovation. Integrated pyrolysis pilot plant is now in operation.

UPM is among the most important users of wood-based raw materials in Finland. The company plans to exploit the potential of several commercial pyrolysis plants in terms of bio-oil production, for its own use as well as for sale to the market, through current and future boiler investments. Metso will be able to market pyrolysis solutions to third parties in the global market. The construction of a commercial-scale demonstration plant will be planned based on the results and experiences garnered from the test runs in 2009 and 2010.

Standard analyses and novel on-line methods will be used through the quality control chain

FUEL CHAIN

Feedstock processing,transporting, feeding

Pyrolysis liquid production,solids removal by centrifugation

Pyrolysis liquid combustionfor CHP in boilers

Forest residue, stumps

On-line moistureanalysis

Gas on-line monitoringOn-line analyses forwater and solids

Water max 28 wt-%solids <0.05 wt-%single-phase liquid

QUALITY CONTROL