AnalyticalOptionsforBiochar

AdsorptionandSurfaceArea
CharacterizationofBiochar
Materials
HughMcLaughlin(Alterna Biocarbon Inc.),
FrankShields(ControlLaboratoriesInc.),
Jacek Jagiello &GregThiele(Micromeritics
AnalyticalServices presenting)

GoalofStudyandPresentation
Toprovidecomparisonandguidancewhen
tryingtodecidewhichtechnique(s)touseto
characterizeBiocharmaterials
TosupporttherecentlyreleasedIBITesting
GuidelineforBiochar
Testsamebiocharsusingresearchand
establishedcommercialanalyticalmethods
Samerawmaterial(woodpellets),twotypesof
biochar,RetortandTLUD,overwiderangeof
productionconditions

Samples
4TLUDCharspreparedat0V,3V,6V,and9V
4RetortCharspreparedat364,500,700,and
900C
SamplespreparedbyAlternaBiocarbon
Homogenized,groundtoacoarsepowder,and
split
CharacterizationperformedbyMicromeritics
AnalyticalServices,ControlLabs,andAlterna

AnalyticalTechniqueschosen
R134aadsorptionmappingusingGACS
analyticaltechnique
Butaneworkingcapacity
N2BETaccordingtoASTMD6556
CO2adsorptioncapacityandmicropore
volume
Watervaporadsorptionisotherms

GACS R134aadsorptiontest
SpecializedtestfromActivatedCarbon
industry measuresactualadsorptionover
widerangeofadsorptionenergies
AdsorbateisR134a=1,1,1,2TetraFluoro
Ethane(RefrigerantinautomobileACsystems)
R134aisdense(heavymolecule),relatively
large,andhardtoadsorbcomparedtoother
probemolecules(N2,CO2,Butane)
Assayadaptedtobiochars lesswellbehaved

GACS R134aadsorptiontest
wt % uptake of R134a on Commercial ACs

100.00%

Std A = 1G Toucan @ 0V = ND
Std B = 1G Toucan @ 3V
Std C = 1G Toucan @ 6V
Std D = 1G Toucan @ 9V

10.00%

1.00%

0.10%
0

50

100

150

200

250

300

tem perature in Celsius

WellbehavedovertheentirerangeoftemperaturesforallTLUDchars

GACS R134aadsorptiontest
wt % uptake of R134a on Commercial ACs

100.00%

Std G = BWP 700C

Std H = BWP 900C
Std F = BWP 500C

10.00%
Std E = R3 #6 @ 364C

1.00%

0.10%
0

50

100

150

200

250

300

tem perature in Celsius

Notaswellbehaved,Highesttemperaturecharmuchlowercapacity

ButaneWorkingCapacity
ASTMD5742 95(2010)StandardTestMethod
forDeterminationofButaneActivityof
ActivatedCarbon(appliedtobiochar)
Weightgainbybonedrycharsampleafter
equilibrationinpurebutaneatoneatm.
Essentiallyrepresentsthetotalmicropore
volumeoftheporousadsorbent
Lowequipmentcostandrelativelyfast
Samplemustbebonedry waterinterferes

ButaneWorkingCapacity
Butane
SampleA TLUD
0V
SampleB TLUD
3V
SampleC TLUD
6V
SampleD TLUD
9V
SampleE Retort
364C
SampleF Retort
500C
SampleG Retort
700C
SampleH Retort
900C

3.77%
5.85%
7.99%
11.28%

2.89%
4.47%
6.27%
3.07%

TLUDchars
wellbehavedandsawan
increaseinbutane
adsorptionwithincreased
chartemperature
Retortchars
decreaseinactivitywith
thehighesttemperature
Retortchar,verysimilarto
R134aGACSresults

BETSurfaceArea
Widelyusedinmanyindustriesincludingcarbon,
carbonblack,activatedcarbon,etc
MultipleASTMandISOmethodsavailable
IS09277
ASTMD6556,C1274,C1069,D3663,.

Calculationoftheexternalsurfaceareaofa
materialfromthevolumeofgasadsorbedat0.05
to0.3relativepressures
Assumesmultilayeradsorptiononnonporoussurface
Pressurerangemodifiedtofitmicroporous materials

N2,BETresults
Initial BET
result
(m2/g)

RepeatBET
result
(m2/g)

SampleA
TLUD0V

216

182

SampleB
TLUD3V

361

333

SampleC
TLUD6V

403

386

SampleD
TLUD9V

472

472

SampleE
Retort

SampleF
Retort500 C

SampleG
Retort700C

389

370

SampleH
Retort900C

80

TLUDchars
IncreaseinBETsurfaceareawithan
increaseinactivationenergy
Reasonablerepeatable
Retortchars
DecreaseinBETsurfaceareawith
highesttemperature
Poorrepeatability
Likelyduetothesmallporesizes
createdduringactivationandtheslow
kineticsofN2gasequilibratinginthe
smallpores
Wehaveseenthismanytimesinpastwith
activatedcarbonsandzeolitesthathave
poresnear5Angstrom
Runtimerangefrom5to24hours

CO2AdsorptionIsothermsat0C
Originallyusedbycarbonindustrytocalculate
poresizeofmicroporousmaterialsbeforehigh
qualityvacuumsystemsandlowpressure
transducersbecamewidelyavailableand
affordable
Notaspopulartodaywithautomated
instruments,butstillusedasanadsorbentprobe
forextremelysmallporecarbons
Fast,Easy
Usesomeuniquemodelingandfittingalgorithms
Dubinin andDFTformicroporevolumeandarea

CO2adsorptionresults
DFTSurface
Area Run1
(m2/g)

DFTSurface
Area Run2
(m2/g)

Dubinin
Micropore
volume(cc/g)

SampleA
TLUD0V

300

287

0.166

SampleB
TLUD3V

330

319

0.182

SampleC
TLUD6V

349

345

0.186

SampleD
TLUD9V

365

360

0.21

SampleE
Retort

103

NA

0.05

SampleF
Retort500 C

251

NA

0.139

SampleG
Retort700C

348

NA

0.188

SampleH
Retort900C

375

NA

0.207

BothTLUDandRetortsamplesseean
increaseinDFTsurfaceareaand
microporevolumewithanincreasein
activationenergy
Therepeatabilityismuchbetterthanwe
experiencedwithN2adsorption
CO2adsorptionisperformedat0Candat
muchhigherrelativepressures,soit
equilibratesmorequicklythanN2
Runtimeontheorderof35hours,but
couldbereducedto12hoursifneeded

CO2adsorptionresults TLUDChars
Isotherm Linear Plot
0V TLUD Gas ifier Biochar Sam ple A
6V TLUD Gas ifier Biochar Sam ple C

3V TLUD Gasifier Biochar Sample B

9V TLUD Gasifier Biochar Sample D

70

60

Quantity Adsorbed (cm/g STP)

50

40

30

20

10

0
0.000

0.005

0.010

0.015

Relative Press ure (p/p)

0.020

0.025

0.030

CO2adsorptionresults RetortChars
Isotherm Linear Absolute Plot
364 C 11-BFPC-D Retort Biochar sample E
BWP700C p8-97 Retort Biochar Sample G

BWP 500Cp8-96 Retort Biochar Sample F

BWP900C p8-98 Retort Biochar Sample H

60

Quantity Adsorbed (cm/g STP)

50

40

30

20

10

0
0

100

200

300

400

Absolute Pressure (mmHg)

500

600

700

800

CO2adsorptionresults
Differential Surface Area vs. Pore Width
0V TLUD Gasifier Biochar Sample A CO2
6V TLUD Gasifier Biochar Sample C CO2
11-BFPC-D Retort Biochar sample E CO2
BWP700C p8-97 Retort Biochar Sample G CO2

3V TLUD Gasifier Biochar Sample B CO2

9V TLUD Gasifier Biochar Sample D CO2
BWP 500Cp8-96 Retort Biochar Sample F CO2
BWP900C p8-98 Retort Biochar Sample H CO2

3,000

Allsampleshavethepresenceof
0.5nmpores;howeverthelowest
temperaturecharsarelessdefined

Differential Surface Area (m/g)

2,500

2,000

1,500

1,000

500

0
4

Pore Width ()

10

WaterVaporAdsorptionIsothermsat25C
Measurestheuptakeand
lossofwatervapor
gravimetricallyusingan
ultramicrobalance
Mimicsbehaviorofbiochar
insoils wateruptake&
releaseversusrelative
humidity
Maymeasurecriticalbiochar
dynamicinsoil need
researchguidance

WaterVaporadsorptionresults
25.00

Increaseinactivationenergywithacorrespondingincreaseinwatervaporadsorption
20.00

0VTLUDSampleA
3VTLUDSampleB
%massgain

15.00

6VTLUDSampleC
9VTLUDSampleD

10.00

5.00

Adsorptionat70%RHusedforcomparisons

Relative Humidty
0.00
0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

95.0

WaterVaporadsorptionresults
14.0

SimilarIncreaseinactivationenergywithacorrespondingincreaseinwatervaporadsorption
RetortSamplesmuchlowertotalwateradsorptionforthehighersurfaceareamaterials
12.0

10.0
RetortSampleE
RetortSampleF500C
8.0
RetortSampleG700C

6.0

4.0

%massgain

RetortSampleH900C

Adsorptionat70%RHusedforcomparisons

2.0

Relative Humidty

0.0
0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

95.0

Tableofresults
A

TLUD0V

TLUD3V

TLUD6V

TLUD9V

Retort
@350C

Retort
@500C

Retort
@700C

Retort
@900C

HMR134a

1.79%

3.64%

4.74%

8.05%

1.84%

4.56%

4.86%

0.68%

FSC3

3.77%

5.85%

7.99%

11.28%

2.89%

4.47%

6.27%

3.07%

N2 BET
(m2/g)

216

361

403

472

389

80

70%RH

7.69%

10.06%

10.99%

12.74%

6.44%

7.76%

9.43%

11.45%

CO2 DFT
(m2/g)

300

330

349

365

103

251

348

375

CO2volads
(cc/g)

53

58

62

68

17

45

62

67

CO2
Micropore
volume
(cc/g)

0.166

0.182

0.186

0.21

0.05

0.139

0.188

0.207

SummaryofallTLUDresults
25.00%

HMR134a

70%RH

FSC3

CO2uporevolDR

500
450

N2BET

20.00%

400
350

15.00%

300
250

10.00%

200
150

5.00%

100
50

0.00%

0
TLUD0V

TLUD3V

TLUD6V

TLUD9V

SummaryofallRetortresults

Correlationto70%RHadsorption
(TLUDChars)

Correlationto70%RHadsorption
(RetortChars)

SummaryCharacterizationResults
Alltechniquesandprobesdidanicejobofmeasuringincreasedcapacity,
surfacearea,oractivityfortheTLUDchars
CO2andWaterweretheonlyprobeswhichmeasuredincreasedcapacitywith
hightemperatureRetortchars
PotentiallyduetokineticsforN2,andsizeofadsorbatemoleculefor
ButaneandR134a
R134a,Butane,andBETreportedsimilardecreasesinactivityforthehighest
temperatureRetortchar
PoresinhightempRetortcharsmaycollapseandexcludeadsorbate
CO2providesafaster,morerepeatableadsorptionisothermandallows
calculationofmicroporedistributionandmicroporevolume
Furtherstudiesandsoilapplicationresearch isneededtodeterminewhich
techniquetrulyprovidesthebestpredictionofperformance

ThankYou
ThankstoDanBurnettofSurfaceMeasurementSystemsforthewatervapor
adsorptiondataandinput
ThankstoHughMcLaughlinfororganizingandleadingthisresearch
ThankstoFrankShieldsfromControlLabs
ThankstoDr.JacekJagiello,colleaguefromMicromeriticsforhisinputand
expertisewithactivatedcarbons