provencher 2015

7/26/2019 Provencher 2015

1/22

1Claisse,2015.AllRightsReserved/TousDroitsRservs.

Chara

cterization

ofCoal

andIt

sBy-prod

ucts

Using

BorateFu

sions

andIC

P-OESAnalyses

ByMarie-veProvenc

her,M.Sc.

Che

mist

USASa

les

Manager

Claisse,

2015

.AllRightsReserve

d/Tous

Dro

its

Rserv

s.


2/22


Solidwas

te

Filter

Coalash

SamplesfromCoalInd

ustry

Coa

lismos

tlyuse

dby

powerp

lan

tstoge

nera

tee

lec

tricity

Emiss

ions

frompower

plan

ts:

o

Gas

(flyas

h)

o

So

lidwas

te(ash)

Why

istraceana

lys

isimportan

t?

o

Ithe

lps

toknowt

hecon

ten

to

fthecoa

lby-pro

duc

ts(coalas

han

dcoa

lflyas

h)

o

Ita

llows

toknow

thecon

ten

to

fthewa

stefrompowerp

lants

(coa

las

han

dcoalf

ly

as

h)foraneco-fr

ien

dlydisposa

l

Coalflyash

Coal


3/22


Ce

rtifiedReferenceMaterials(C

RMs)

Coal

Coalash

Coalflya

sh

NCSFC28127

VS-7177-95

EOP12-1-02

China

Ru

ss

ia

Czec

hRepu

blic

Al

3.4

7

14

.3

16

.1

Si

5.6

1

27

.4

22

.9

3

CRMs

from

coa

lindus

try

H

ighs

ilicaan

da

lum

inac

on

ten

t

S

amp

leprep

ara

tionmet

ho

d

Ac

iddiges

tion

(no

te

fficien

t)

Hars

hac

id(HF)(no

ten

tire

lysa

fe)

Fus

ion


4/22


No

rms

AS

TMD6349

o

Samplepreparation:

Boratefus

ion

Aciddiges

tion

(HF/HNO

3/HCl)

o

ICP-OES

o

Al,Ba,Ca,Fe,K

,Mg,

Mn,Na,

P,S

,Si,Srand

Ti

AS1038.14.1

o

Sample

preparation:

borat

efusion

o

AA

o

Al,Ba,

Ca,Fe,K

,Mg

,

Mn,Na

,P,

S,Si,Sr,T

i

andZn


5/22


Coal

Coalash

Coalfly

ash

NCSFC28127

VS

-7177-95

EOP12-1-02

China

Russ

ia

Czec

h

Repu

blic

LOI

74

.3%

0.4

2%

0.29

%

R

ampup

to500Cfor1

hour

R

ampup

to750Cfor2

hours

H

olda

t750Cfor

2hours

Pretreatmen

tofSamples


6/22


SamplePrep

arationby

BorateFusion

XRF

Analys

is

ICP

and

AA

Ana

lysis


7/22


Sa

mplePrep

arationbyBorateF

usion

Ina

Pt/Au(95%/5%)

crucible:

o

0.1

00go

fas

hed

samp

le

o

0.1

50g

LiNO

3

o

1.0

00g

LiM/1

.5%

LiBr

Kee

pinmind:

o

Lowsamp

le/fluxra

tio

(1/10)foranopt

imize

dsamp

le

disso

lution

o

Thenon-we

ttingagen

ta

llowsacomp

letepouring

o

Silicaan

da

lum

inaareveryso

lubleinlithium

me

tabora

te


8/22


1.

Manual

Meekerburn

erandrisingstand

Mufflefurnac

e

Homemade

2.Automatic

Gasfired

Electric

Fu

sionTechniqueInst

ruments


9/22


ClaisseAutomaticFluxers

GASELECTRICM4TMClaisse

fluxe

r

LeNeo

Claisse

fluxer

Eagon2Claisse

fluxer

The

Ox

Claisse

fluxe

r

Propane

&N

atura

lGas


10/22

10

Claisse,2015.AllRightsReserved/TousDroitsRservs.

Au

tomatedF

usion

L

eNeo

fusionins

trument

O

nefusionpositio

n

P

rogrammablepa

rameters(tempera

ture,

dura

tionan

dag

ita

tion

):

o

Ox

ida

tions

tepat

800C

o

Fas

ttempera

ture

ramp-up

(up

to1200

C)

o

The

fus

ions

teps

arecomp

letedin7m

inu

tes

Steps

Duration(m

in)

Rockingangle

Rockingspeed

Temperature(C)

O

xidation

2

0

0

800

Fusion

1

0

0

1000

Fusion

1

0

0

1050

Fusion

1

20

15

1050

Fusion

1

30

20

1050

Fusion

1

40

30

1050

P

ouring

Stirring

6


11/22

11


Au

tomatedD

issolution

The

disso

lution

iscomp

lete

din6m

inutes:

o

Completepo

uring

o

90mLof10%

HNO

3

o

Magneticagitation

Steps

Duration(m

in)

Rockingangle

Rockingspeed

Temperature(C)

O

xidation

2

0

0

800

Fusion

1

0

0

1000

Fusion

1

0

0

1050

Fusion

1

20

15

1050

Fusion

1

30

20

1050

Fusion

1

40

30

1050

P

ouring

Stirring

6


12/22

12


Ma

nualDilution

C

omp

leteto

100m

L

A

ddthe

interna

ls

tan

dar

d

D

ilution

1in2

F

ina

lvo

lume

at200m

L

0.5

%oftotald

issolvedsa

lt


13/22

13


Instrumentation

o

PerkinElmer

Optima

7300D

VICP-OES

Analysis

o

Matrix-matchedcalibrationcur

ve

o

Internalstand

ardsadded

Nebulizer

Gem

TipCross

flow

Spraychamber

Sco

tt

Injector

Alum

ina

2mm

i.d

.

RF

1500W

Argonflow

Plasma:

16L/min

Ne

bu

lizer:

0.8

L/min

Aux

iliary:

0.4

L/min

Sampleflowrate

1.0

mL/min

An

alysisby

ICP-OES


14/22

14


Elementsofinteres

t

Associatedinternalstandards

Both

Elem

ents

Wavelength

Io

nization

p

otential

Internal

standards

Wavelength

Ionization

potential

Ionization

state

View

ing

mode

A

l

237.3

13

6.0

Ga

294.3

64

6.0

I

Axial

Ca

422.6

73

6.1

Eu

381.9

67

5.7

II

Ra

dial

Fe

238.8

63

7.9

Re

197.2

48

7.9

II

Axial

K

766.4

90

4.3

Rb

780.0

23

4.2

I

Axial

Mg

279.0

77

7.6

Re

197.2

48

7.9

II

Axial

Na

589.5

92

5.1

Ga

294.3

64

6.0

I

Ra

dial

S

i

252.8

51

8.2

Te

214.2

81

9.0

I

Axial

T

i

337.2

79

6.8

Eu

381.9

67

5.7

II

Axial

Inte

rnalstandard

associatedwiththeelement:

Similar

ion

izatio

npo

ten

tia

l

Similar

ion

izatio

ns

tate

Int

ernalStan

dards


15/22

15


Ca

libration,MethodDetectionLimits

(M

DLs)andLinearity

Elem

ents

Wavelength

(nm)

View

MDL

(mg/L)

Calibrationrange

Correlationcoefficient

(pts=5)

(Min)

(Max)

A

l

237

.313

Ax

ial

0.0

7

13

.8

275

1.0

000

B

a

413

.065

Ax

ial

0.0

06

0.2

5

5.0

0

1.0

000

C

a

422

.673

Ra

dial

0.1

6.0

0

115

1.0

000

F

e

238

.863

Ax

ial

0.0

2

6.2

5

125

1.0

000

K

766

.490

Ax

ial

0.0

02

0.9

00

18

.0

0.9

997

M

g

279

.077

Ax

ial

0.0

07

0.8

80

17

.5

1.0

000

M

n

293

.305

Ax

ial

0.0

01

0.1

38

2.7

6

1.0

000

N

a

589

.592

Ra

dial

0.0

5

0.2

80

5.5

0

1.0

000

P

177

.434

Ax

ial

0.0

3

1.6

0

30

.0

0.9

995

S

181

.975

Ax

ial

0.0

6

2.8

0

55

.0

1.0

000

S

i

252

.851

Ra

dial

0.0

7

15

.0

300

1.0

000

S

r

460

.733

Ax

ial

0.0

02

0.3

30

6.5

0

0.9

999

Ti

337

.279

Ax

ial

0.0

02

2.8

0

55

.0

1.0

000

Z

n

213

.857

Ax

ial

0.0

03

0.1

50

3.0

0

1.0

000


16/22

16


T

hemethodhas

beentestedwith3differentty

pesofsamples

:

o

Flyas

h

o

Coa

las

h

o

Coa

l

A

ccuracyandprecisionwerecalculatedbased

onthecertified

r

eferencevalue

ofeachCRM(Al,Ca,

Fe,

K,M

g,

Na,

SiandT

i)

R

ecoverywasc

alculatedwiths

amplesspiked

beforefusion(B

a,

K

,Mn,

P,

S,

Sra

ndZn)

Re

sults

Fly

ash

Coalash

Co

al


17/22

17


PrecisionandAccuracy

inBrown

CoalFlyAsh

EOP12

-1-02

Elements

Certifiedvalues

(%)

Experimentalvalues

(%)n=10

MDL

(%)

Precisiont0

,975;9

(%)

Accuracy

(%)

RS

D

(%

)

Al

16.1

16.3

0.0

1

0.1

98.7

0.5

Ca

1.4

9

1.4

4

0.0

2

0.0

4

96.5

3.9

Fe

5.1

7

5.2

1

0.0

03

0.0

2

99.2

0.5

K

0.6

51

0.6

30

0.0

004

0.0

11

96.7

2.4

Mg

0.5

81

0.6

23

0.0

01

0.0

02

93.0

0.5

Na

0.3

61

0.3

7

0.0

1

0.0

1

97.6

3.5

Si

22.9

23.8

0.0

1

0.4

96.3

3.7

Ti

3.6

1

3.4

4

0.0

003

0.0

1

95.3

0.5

Dilution

fac

tor:

1994

n=

10


18/22

18


Precisionan

dAccurac

yinCoal

NCSFC28127

Elements

Certifiedvalues

(%)

Experimentalvalues

(%)n=10

MDL

(%)

Precisiont0

,975;9

(%)

Accuracy

(%)

RS

D

(%

)

Al

3.4

7

3.3

7

0.0

03

0.0

3

97.1

1.2

Ca

1.8

8

1.8

9

0.0

06

0.0

4

99.3

2.8

Fe

1.0

2

1.0

5

0.0

008

0.0

1

97.4

1.0

K

0.2

9

0.2

81

0.0

001

0.0

05

97.0

2.5

Mg

0.2

8

0.2

94

0.0

004

0.0

02

94.7

0.8

Na

0.0

52

0.0

52

0.0

02

0.0

01

99.6

2.2

Si

5.6

1

6.0

5

0.0

04

0.0

6

92.2

1.3

Ti

0.1

8

0.1

73

0.0

0008

0.0

02

96.4

1.4

Dilution

fac

tor:

513

n=

10


19/22

19


Precisionan

dAccurac

yinCoal

Ash

VS717

795

Elements

Certifiedvalues

(%)*

Experimentalvalues

(%)n=10

MDL

(%)

Precisiont0

,975;9

(%)

Accuracy

(%)

RS

D

(%

)

Al

14.3

3

14.0

0.0

1

0.1

97.7

1.3

Ca

3.4

9

3.7

0

0.0

2

0.0

6

94.0

2.4

Fe

3.8

3

3.7

3

0.0

03

0.0

3

97.3

1.0

K

0.4

9

0.4

46

0.0

004

0.0

06

91.0

1.9

Mg

0.8

93

0.8

74

0.0

01

0.0

09

97.9

1.5

Na

0.1

0

0.1

1

0.0

1

0.0

1

97.6

3.1

Si

27.4

3

28.6

0.0

14

0.4

95.7

2.1

Ti

0.3

6

0.3

57

0.0

003

0.0

03

99.3

1.2

*MeasuredasAlbutreportedasAl2O

3onthecertificateofanalysisprovided

withmaterial

Dilution

fac

tor:

1992

n=

10


20/22

20


Re

coveryforthe3CRMs

EOP12-1-02

(browncoal

flyash)

NCSFC28127

(coalash)

VS7177-95

(coal)

Elem

ents

Spiked

values

Recovery

RSD

Spiked

values

Recovery

RSD

S

piked

values

RecoveryR

SD

mg/L

%

%

mg/L

%

%

mg/L

%

%

Ba

1

102

0.4

1

102

1

1

103

0.2

K

3

91

3

5

102

2

3

91

4

Mn

1

102

1

2

100

0.7

1

104

0.6

P

1

99

1

1

103

1

1

101

3

S

1

97

3

5

100

1

1

96

3

Sr

1

96

1

1

100

0.9

1

98

3

Zn

1

100

0.7

1

101

0.9

1

101

1

n=

5


21/22

21


Co

nclusion

G

reatoveralla

ccuracy:

o

Minimum(smallervalue)91.0%

forK

o

Average96.6

2.3

%

G

reatoverallrecovery:

o

Minimum91%

forK

o

Average99.5

3.6

%

I

tisappropriatetouseLeNeoinstrumenttopreparecoal

s

amplesforICP-OESanalys

isinaccordan

cewithindustry

n

orms


22/22

22


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.com

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isse.com

provencher 2015

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