WTERT R h U d tWTERT Research Update Gasification of ... · PDF fileWTERT R h U d tWTERT Research Update Gasification of Biomass ... “The next turn of the market wheel may reward

WTERT R h U d tWTERT Research UpdateGasification of Biomass

Solid Carbon Conversion

Marco J. CastaldiDepartment of Earth & Environmental EngineeringHenry Krumb School of Mines, Columbia University

WTERT 2008 Bi-Annual MeetingColumbia UniversityNew York, NY 10027

WTERT 08, New York, NY

October 16th and 17th

The Future

• Fossil Fuels will play smaller role

• Renewable / indigenous fuels will

become more prominentbeco e o e p o e t

• Carbon management is here to stay


The NeedThe Need

• Carbon Neutral Energy ProductionCarbon Neutral Energy Production• Clean chemical (H2) Production

Z i i th CO t ti• Zero emissions more than CO2 sequestration• Reduce the dependence on single feedstock

• Indigenous source of fuel, distributed sources

• Power and chemicals produced from waste/biomass must be economically attractive as compared to current sources.


Investment (wall Street)• Socially responsible investing• Emissions control (CO2)Emissions control (CO2)• Eco-friendly business practices

W ld E i F• World Economic Forum– Businesses need to reduce the negative impact on

h ithe environment“Many companies are now discovering that there my a be a strong correlation between ‘doing good’ and ‘doing well’”between doing good and doing well

“The next turn of the market wheel may reward companies with strong free cash flow as well as innovative companies thinking green”


Alger Market Commentary March 31, 2007

Bioenergy

Source: IEA


Municipal Solid Waste (MSW)• ~ 220 million tons of waste generated per year (U.S.)• Landfills are filling up• Disposal costs and energy costs are going up• Greenhouse gas initiatives (RGGI, etc)

•Waste as fuel emits 2/3 less CO2 than fossil fuel

Potential to replace ~ 20% of oil imports per year

Burning is good (WTE); instead of oil use waste

oil imports per year

Burning is good (WTE); instead of oil use waste• Gasification gives options

•choice of products – Heat, fuels, chemicals


Chemicals From WasteChemicals From Waste• Military MISER program

– Trash/Biomass/Solid hydrocarbons to fuels– Trash/Biomass/Solid hydrocarbons to fuels

• American Chemical Society (ACS)– Letters to the editor – “chemicals from waste”

• C&EN April 2006

• Discover Magazine –– “DATA” Section : The Ultimate Garbage Disposal

• How to turn trash into clean energy – Geoplasma UnitHow to turn trash into clean energy Geoplasma Unit– 160 MW by 2009, St. Lucie County, Florida

• EnerChem/City of Edmonton 2008


• EnerChem/City of Edmonton - 2008

CO2 & Waste / BiomassEnhanced gasification


Catalytically Controlled Reaction y yGasifier (CRG Process)

O2

COsplit

O2

CoalH O2

CO2(optional)

H2

H2

CO H2

COout

H2

COH O2

AshH2

AshSeparator

H OSep.

2

CO+O to CO2 2

CO2

SOFCCO2

Carbon2

COH OAsh

2

H O2CO

Ashto waste stream H O2 CO2

recycle2


H O Make up (optional)2

Castaldi MJ, Dooher JP. Int J Hydrogen Energy (2007), 37, 4170 - 4179

CRG Aspen™ SimulationCRG Aspen Simulation

CO PROD

CO-SPLIT

CO-ELECCMBSTOR

O2-COMB

COMBOUT

CO2RECYL

CO2EXHST

CO-PRODCO-COMB

CO2RETRN

C-IN

REF-PROD

H2-SEP

COOLDOWN COOLPROD H2O-PROD

REFORMERWATER-IN

H2-PROD


Castaldi MJ, Dooher JP. Int J Hydrogen Energy (2007), 37, 4170 - 4179

1.2H2 Production, basis:0.5 kmol/hr C

ate

(kg/

hr)

0.8

1.0s/c:1.0, r:0

Baseline simulation results of energy balance and hydrogen

H2 F

low

ra

0 2

0.4

0.6generation for CRG process

Conventional Gasifier

0.0

0.2

10

20

Energy Requirements

H2O/C = s/c, CO2 recyc = rConventional Gasifier

H2 0.7 kg/hrCO2 ~ 15%

CRG P

y (M

J/hr

)

0

10Energy req'd by gasifierbalanced by CO combustion

CRG ProcessH2 0.85 kg/hrCO2 ~ 1.5%

e- ~13 kW/kmol C

Ene

rgy

-20

-10s/c:1.0, r:0CO Combustion ~48%

WTERT 08, New York, NY CO Split (to combustor)

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-30

Castaldi MJ, Int J Hydrogen Energy (2007), 37, 4170 - 4179

1.0


s/c:1.0, r:0.25

Flow

rate

(kg/

hr)

0.6

0.8s/c:1.0, r:0

H2 F

0.2

0.4

H2O/C = s/c, CO2 recyc = r

Comparison of baseline and 25% CO2 recycle to the

reformer0.0

10

20

Energy Requirements

Energy req'd by gasifierCRG Process

H 0 95 kg/hr

nerg

y (M

J/hr

)

-10

0

s/c:1.0, r:0

balanced by CO combustionH2 0.95 kg/hrCO2 ~ 1.5%

e- ~13 kW/kmol CCO Combustion ~42%

E

-20

s/c:1.0, r:0.25


CO Split (to combustor)

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-30


Experimental Feedstock Tested

BiomassCoalWaste


Experimental Mass Decomposition Curve

1.00•250-400oC: Primary Reaction

• Bulk mass loss• Devolatilization and pyrolysis

0.60

0.80

actio

n

GrassesGrasses

•400-700oC: Secondary Reaction• Ligno-cellulosic gasification

Coals

0.40

Mas

s Fra

•700-900oC: Tertiary Reaction • Oxygen in feedstock & steam react with

lid b

0 00

0.20

WoodsWoods

solid Carbon• Recycled CO2 begins char burnoutMSW

0.000 200 400 600 800 1000

Temperature oC •950 - 1000oC Mass burnout complete• Higher residual correspond to lower


g plignin content

Butterman and Castaldi, Env. Eng. Sci (2007) 22, 31-44

CO2 Impact on Coal

• Decrease in H2d ti ith COproduction with CO2

• Increase in CO production with CO2


MSW DATAMSW DATAMass % vs Temp for Varius Amounts of CO2100

80 20

25Area 1: water volatilization

20

25

Area 2: biomass degradation

ass %

60

5

10

15

5

10

15

Ma

40

20% CO210% CO2

700 750 800 850 900 950 10000

Area 3:

700 750 800 850 900 950 10000

0

20 5% CO22.5% CO2Inert1% CO2

Area 3: petrochemical degradation

Area 4: boudouard reaction (C O2 + C 2C O)


Temperature (oC)0 200 400 600 800 1000

0

CO i t ifi ti d tCO2 impact on gasification products1.00

CO2 Variation0.020

CO2 Variation

0-1)

0 40

0.60

0.80 0% 5%10%15%20%30%

40%

2

1 )

0.015

0% 5%10%15%20%40%50%

CO2 Variation

Mol

e Fr

actio

n (1

0

0.04

0.20

0.40 40%50%

ole

Frac

tion

(10-1

0.010

Increasing CO2

Increasing CO2

CO

M

0 01

0.02

0.03

H2 M

o0.005

Increasing CO2

Reactor Temperature (oC)

200 400 800 900 10000.00

0.01

R T (oC)

600 700 800 900 10000.000


Reactor Temperature ( C)Fi 1 H d i i h CO ifi i

Reactor Temperature (oC)

CO increases with CO2 H2 decreases with CO2

H2/CO (Syngas) Tuning• Fuels • Chemicals• Combustion

3.0 SOFC operation• Combustion• Fuel cells

2.5

p

Gas Turbine Combustion – Low NOx operation/good stability

1.5

2.0

H2/C

O

Fisher Tropsch – petroleum/diesel fuels

Fisher Tropsch – Fe-based Catalyst – low molecular weight

1.0

H Co-based – more aromatic

specialty chemicals - dimethyl ether

0.0

0.5


0 10 20 30 40 50

%CO2

Structural Components of BiomassCellulose- the main structural component of biomass, linear crystalline polymer of glucose held together by β-glycosidic g g y β g ylinkages strengthened by H-bonding between chains

Hemicellulose- short highly branched, less rigid and more easily hydrolyzed, amorphous polymer of 5 and 6-carbonamorphous polymer of 5 and 6-carbon sugars

Lignin- the structural component of biomass that strengthens the cell wall and cements the cells together, high


MW, highly cross-linked aromatic

Lignin Decomposition

H2

HH2

CH4Methane producing speciesVinyl Ionic Phenoxy

LigninCH4

CH4

CH2

O

HO

CHHC

CH

CH2

CH CH

Continued Carbon enrichment

CO

O

HOHO

C

O

C

HC

CHHC

CH2

2-FuraldehydeDecarboxylation

Methylation and


CH2

C

CH2

Lignin CharMethylation andDehydrogenationOf Lattice Structure

Cellulose DecompositionTrehalose Amylose

Levoglucosan

e a oseDehydroxylationPolymerization

(Methanol solubleOligosaccharides)

(Water solublePolysaccharides and

Furans andb l )

Furfural undergoes decarbonylationCellobiose

Carbonyls)

OO

Cellobiose

Carbonized Cellulose CharDevolatilizationNo Char formation

CH2

C

C

O

CH CHLow MW


OCH CH

Low MWVolatilesCO,CO2,CH4,H2

Major Gasification Reactions

Water Gas Shift Steam GasificationLow Temperature High TemperatureWater Gas Shift

CO + H2O CO2 + H2

M th ti

C + H2O H2 + CO

BoudouardMethanation

C + 2H2 CH4

C + CO2 2CO

2CO + 2H2 CH4 + CO2

CO + 3H2 CH4 + H2OChar Burnout: O (Biomass/Steam)C + ½O2 CO

Steam GasificationC + H2O H2 + CO

Reverse Water Gas ShiftCO + H CO + H O


C H2O H2 CO CO2 + H2 CO + H2O

CO Comparison


Butterman and Castaldi, Indus. & Eng, Chem. Res, (2007) 47, 8875-8886

H2 Comparison


Butterman and Castaldi, Indus. & Eng, Chem. Res, (2007) 47, 8875-8886

CH4 Comparison

WTERT 08, New York, NY Butterman and Castaldi, Indus. & Eng, Chem. Res, (2007) 47, 8875-8886

Value: Enhanced Char Burnout With CO2

• Identical time on stream, reaction

temperature profile, total flow rate

• Physical evidence of more efficient

gasification with COgasification with CO2Walnut Shells: 0% CO2 Walnut Shells: 30% CO2

Douglas Fir: 0% CO2

• Observed for all

Douglas Fir: 30% CO2

Poplar: 0% CO2 Poplar: 34% CO2


• Observed for all

samples testedButterman and Castaldi, Indus. & Eng, Chem. Res, (2007) 47, 8875-8886

C C i COChar Pore Development- Enhanced Char Burnout With CO2

LigninLigninLignin Lignin

100% CO2

1oC/min

Lignin

100% CO2

1oC/min

Lignin

0% CO2 -H2O/N2

1oC/min,


22-930oC 22-860oC 22-860oC

Cellulose/Lignin SeparationCellulose/Lignin Separation100

CO Gasification100

CO Gasification• Separation of lignin from

cellulose, CO2 processes lignin more efficiently than

70

80

90CO2 Gasification

Lignin○ 1 ° min-170

80

90CO2 Gasification

Lignin○ 1 ° min-1steam

dual

Mas

s (%

)50

60

70 ○ 1 min 1

● 100 ° min-1

dual

Mas

s (%

)50

60

70 ○ 1 min 1

● 100 ° min-1

Res

i

20

30

40

Cellulose

Res

i

20

30

40

Cellulose

200 400 6000

10▲ 1 ° min-1

Δ 100 ° min-1

200 400 6000

10▲ 1 ° min-1

Δ 100 ° min-1


Reactor Temperature (oC)Reactor Temperature (oC)

SEM - Douglas Fir Char Fiber Enhanced i d i ifi imicropore structure during steam gasification

Increased porosity following thermalthermal treatment


Conclusions

• Data quantitatively matches Simulation

• CO2 injection enhances CO productionT > 700oC lti i i d h b t• T > 700oC resulting in improved char burnout

• Less residual ash, especially carbon

•CO production near 400oC marks transition between the two thermal•CO production near 400 C marks transition between the two thermal degradation regimes

• 250-400oC – Local maxima of CO production• T > 700oC – Steady increase in COT 700 C Steady increase in CO

• H2 production had two regions of abrupt production • 550-575oC for herbaceous• 675-725oC for woody feedstocks

• Coal and MSW follows trends of biomass


• CO2 accesses the recalcitrant Char more effectively than steam

AcknowledgementsgDr. Heidi Butterman – Post-Doc

Dr Eilhann Kwon PhD Student/Post DocDr. Eilhann Kwon – PhD Student/Post-Doc

Kelly Westby – Undergraduate EEE student

Professor John Dooher – Adelphi University


Poster Session

Defining Sustainability

1 S t i bilit i th f ti i t h i th d t d

Many equate sustainability with no emissions, or minimized raw material usage, with considering the impacts at the boundaries – avoided emissions or decreased energy use

1. Sustainability is a path of continuous improvement, wherein the products and services required by society are delivered with progressively less negative impact upon the Earth – IfS:AIChE

2. Sustainability is an attempt to provide the best outcomes for the human and natural environments both now and into the indefinite future. - Wikipedia

3. Sustainable development as development that "meets the needs of the present without compromising the ability of future generations to meet their own needs". It relates to the continuity of economic, social, institutional and environmental aspects of human society, as well as the non-human environment -Brundtland Commission

Sustainability is not a way to raise taxes – NYC mayor, $8 to enter city by car during working hours


Currently“The nature of environmental issues is changing from a regulatory to a resource focus” R. MacLean, Env. Protec. April 2003, P.12

• Education

P bli A t i f ti

g y f

• BP Re-staffing for environmental innovation

– Public Access to information

• Environment resource utilization• Walmart Supply chain vendors

“20 chemicals of concern• Home Depot Eco-Label

– Concentrators and Dilutors

• Climate change economic issue

• Carpet Recyclers profitable• GE wind power, clean water• NSF new directorate (EBW)• Venture Capital Niche

energy/environment


Alternative EnergyAlternative Energy• The world is sensitive to energy supply (new Paradigm)

− Security, Procurement supply chain disruptions

• Two-fold increase in energy consumption (demand)• From 402 exajoules to 837-1041 over next 40 years.

• CO2 atmospheric concentrations are rising (environment)− The need for separating carbon dioxide from the product gases

and plant effluent in order to prevent it from entering the t hatmosphere.

− Space constrained or preferred land use


• Power / heat sectors are extremely inefficient

Scale of the IssuePower / heat sectors are extremely inefficient

• ~60% of energy is wasted!• better power cycles and materials will help• All fuels are needed!

• Heat generation produces 2/3 of all CO2 emissions

• Better thermal conversion


systems needed• Better Fuels needed!

Energy from Waste• WTE conserves fossil fuels by generating electricity. (Energy)WTE conserves fossil fuels by generating electricity. (Energy)

– 1 ton of waste combusted = 45 gallons of oil or 0.28 tons of coal– Most WTE facilities in U.S. process between 500 and 3,000 tons of waste per day– Electricity for 2.8 million homes

• WTE facilities process 14% of the MSW in the United States. (Health)– Trash-disposal needs about than 37 million people

• WTE facilities meet some of the world's most stringent standards. (Environmental, local)– Achieved compliance with new Clean Air Act pollution control standards in 2000p p– EPA data :dioxin emissions now account for less than 0.5% of dioxin emissions

• WTE facilities reduce greenhouse gas emissions. (Climate, global)– EPA estimates :WTE facilities prevent 33 million metric tons of CO2 per year avoided

WTE f iliti l t t (L d)• WTE facilities save real estate. (Land)– They reduce the space required for landfills by about 90%

• WTE is compatible with recycling. (Resource Minimization)– Communities served by WTE recycle 35% of their trash, compared to 30% for the general

population.– Annually removes more than 700,000 tons of ferrous materials– Nearly 3 million tons of WTE ash is reused as landfill cover, roadbed, or building material.

• WTE facilities provide economic benefits. (Economic)


WTE facilities provide economic benefits. (Economic)– WTE is a $10 billion industry employs ~ 6,000 American workers annual wages ~ $400 million

Boundaries and interfaces of WTE cut across all sustainable fronts

BioenergyS i bl b l h d h i l f d k• Sustainable carbon neutral power, heat and chemical feedstocks.

• Potential to provide ~ 15% of energy demand.• Gasification

• Lower PM, NOx, and SO2, than combustion• Steam addition – Increased concentration of H2• CO2 usage – enhanced char conversion and less residue for landfill.• Provides reagents (CO & H2) for synthetic fuel/chemical production

Estimations vary widelyEstimations vary widely due to land availability and crop yields.

One piece of the alternative energy future technologies


1.0


s/c:1.0, r:0.25

owra

te (k

g/hr

)

0.6

0.8s/c:1.0, r:0

s/c: 1.0, r:0.5

H2 F

lo

0.2

0.4

H2O/C = s/c, CO2 recyc = rCO recycle comparison for0.0

10

20

Energy Requirements

H2O/C s/c, CO2 recyc r

Energy req'd by gasifier

CO2 recycle comparison for steam to carbon ratio of 1.0.

Tradeoff: energy neutral vs

nerg

y (M

J/hr

)

-10

0

s/c:1.0, r:0

balanced by CO combustionH2 production

En

-20

10

s/c:1.0, r:0.25s/c:1.0, r:0.5


CO Split (to combustor)

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9-30

s/c:1.0, r:0.5


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WTERT R h U d tWTERT Research Update Gasification of ... · PDF fileWTERT R h U d tWTERT Research Update Gasification of Biomass ... “The next turn of the market wheel may reward