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Recovering Rare Earth Metals from Coal Fly Ash Ross Taggart Department of Civil & Environmental Engineering 4 March 2015 1 2015 World of Coal Ash (WOCA) Conference in Nasvhille, TN - May 5-7, 2015 http://www.flyash.info/

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Page 1: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Rec

ove

rin

g R

are

Eart

h

Met

als

fro

m C

oal

Fly

Ash

Ro

ss T

ag

ga

rt

De

pa

rtm

en

t o

f C

ivil

& E

nv

iro

nm

en

tal

En

gin

ee

rin

g

4 M

arc

h

20

15

1

2015

Wo

rld

of

Co

al A

sh (

WO

CA

) C

on

fere

nce

in N

asvh

ille,

TN

- M

ay 5

-7, 2

015

htt

p:/

/ww

w.f

lyas

h.in

fo/

Page 2: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Ou

tlin

eB

ackg

rou

nd

◦R

are

Eart

h E

lem

ents

◦C

oal

Fly

Ash

Ob

ject

ives

an

d H

ypo

thes

es

Res

earc

h A

pp

roac

h a

nd

Met

ho

ds

◦A

sh c

har

acte

riza

tio

n

◦Se

qu

enti

al e

xtra

ctio

ns

and

XA

S

◦Ex

trac

tio

n m

eth

od

s

Inte

llect

ual

Mer

it a

nd

Bro

ader

Imp

acts

2

Page 3: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Rar

e Ea

rth

Ele

men

tsC

on

sist

of

lan

than

ides

an

d y

ttri

um

No

t p

arti

cula

rly

rare

, ju

st d

iffu

se◦

10

3ti

mes

mo

re a

bu

nd

ant

than

pre

cio

us

met

als

◦C

rust

al c

on

cen

trat

ion

(2

20

pp

m)

com

par

able

to c

arb

on

(2

00

pp

m)

Hea

vy r

are

eart

hs

less

co

mm

on

3

Page 4: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Cri

tica

l Mat

eria

lsR

EE in

def

ense

, en

ergy

, an

d e

lect

ron

ics

ind

ust

ries

:◦

Gu

idan

ce/c

on

tro

l sys

tem

s

◦Pe

tro

leu

m c

rack

ing

cata

lyst

s

◦Pe

rman

en

t m

agn

ets

◦LE

Ds/

glas

s ad

dit

ive

◦M

oto

rs/g

ene

rato

rs

◦C

atal

ytic

co

nve

rter

s

◦Fl

at p

anel

dis

pla

ys

◦H

ard

dri

ves

◦B

atte

ries

◦H

ybri

d/e

lect

ric

veh

icle

s

4

Page 5: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

REE

Cri

tica

lity

5

Cla

ssif

icat

ion

s fr

om

Se

red

in(2

01

0)

The

“Bal

ance

Pro

ble

m”

◦R

EE u

tilit

y d

oes

no

t m

atch

ab

un

dan

ce

◦Sh

ort

age

of

crit

ical

REE

Co

nve

nti

on

al o

res

hav

e lo

w C

/E r

atio

(o

utl

oo

k co

effi

cien

t)

Cat

ego

rySy

mb

ol

Nam

e

Cri

tica

l

Nd

Neo

dym

ium

EuEu

rop

ium

TbTe

rbiu

mD

yD

ysp

rosi

um

YYt

triu

mEr

Erb

ium

Un

crit

ical

LaLa

nth

anu

mP

rP

rase

od

ymiu

mSm

Sam

ariu

mG

dG

ado

liniu

m

Exce

ssiv

e

Ce

Cer

ium

Ho

Ho

lmiu

mTm

Thu

lium

YbYt

terb

ium

LuLu

teti

um

Page 6: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Rar

e Ea

rth

Pro

du

ctio

n

Du

an

d G

raed

el(2

01

1) a

nd

htt

p:/

/ww

w.c

net

.co

m/n

ews/

dig

gin

g-fo

r-ra

re-e

arth

s-th

e-m

ines

-wh

ere-

iph

on

es-a

re-b

orn

/

6

Page 7: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Sup

ply

an

d D

eman

d2

01

3:

86

%o

f R

EE p

rod

uct

ion

to

ok

pla

ce in

Ch

ina

Ch

ina

con

tro

ls 4

8%

of

glo

bal

REE

su

pp

ly

20

10

: d

eman

d e

xcee

ds

sup

ply

by

30

00

T

Dem

and

pro

ject

ed t

o in

crea

se c

on

sist

entl

y

7

Co

un

try

20

10

Pro

du

ctio

n (

t)2

01

1 P

rod

uct

ion

(t)

Esti

mat

ed

Re

serv

es

(t)

Ch

ina

13

0,0

00

13

0,0

00

55

,00

0,0

00

Un

ited

Sta

tes

0*

0*

13

,00

0,0

00

Res

t o

f w

orl

d3

,00

03

,00

04

2,0

00

,00

0

Tota

l1

33

,00

01

33

,00

01

10

,00

0,0

00

Page 8: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Ou

tlin

eB

ackg

rou

nd

◦R

are

Eart

h E

lem

ents

◦C

oal

Fly

Ash

Ob

ject

ives

an

d H

ypo

thes

es

Res

earc

h A

pp

roac

h a

nd

Met

ho

ds

◦A

sh c

har

acte

riza

tio

n

◦Se

qu

enti

al e

xtra

ctio

ns

and

XA

S

◦Ex

trac

tio

n m

eth

od

s

Inte

llect

ual

Mer

it a

nd

Bro

ader

Imp

acts

8

Page 9: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Envi

ron

men

tal H

azar

d5

3.4

mill

ion

to

ns

pro

du

ced

an

nu

ally

in t

he

U.S

.

Ove

r 4

0%

is r

ecyc

led

, pri

mar

ily in

cem

ent

The

rem

ain

ing

30

mill

ion

to

ns

is la

nd

fille

d o

r h

eld

in

wet

ash

imp

ou

nd

men

ts◦

Oft

en u

nlin

ed

◦P

ron

e to

fai

lure

Toxi

c tr

ace

ele

me

nts

: A

s, S

e, C

r, C

d, P

b, e

tc.

Co

nta

min

ate

gro

un

dw

ater

an

d s

urf

ace

wat

ers

9

Page 10: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Ash

Sp

ills

TVA

Kin

gsto

n F

oss

il P

lan

t in

D

ecem

ber

20

08

◦3

.7 m

illio

n m

3o

f m

ixed

fly

as

h a

nd

bo

tto

m a

sh r

elea

sed

◦3

00

acr

es c

on

tam

inat

ed

Dan

Riv

er (

Eden

, NC

) in

Fe

bru

ary

20

14

◦3

0,0

00

-39

,00

0 t

on

s o

f as

h

rele

ased

10

Page 11: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Stra

tegi

c M

etal

s in

Ash

Som

e as

hes

exc

ee

d o

re g

rad

e (

ove

r 1

00

0 m

g/k

g)

NIS

T SR

M 1

63

3b

has

42

0 m

g/k

g R

EE

Enri

ched

10

x d

uri

ng

com

bu

stio

n

Pre

ced

ent

for

met

al r

eco

very

fro

m c

oal

an

d f

ly a

sh◦

Ura

niu

m s

ou

rce

aft

er W

orl

d W

ar II

◦G

erm

aniu

m s

ou

rce

sin

ce 1

96

0s

◦A

lum

inu

m r

eco

very

res

earc

h in

19

70

s an

d 1

98

0s

◦R

ecen

t ga

lliu

m r

eco

very

fro

m f

ly a

sh

11

V.V

. Ser

edin

, S. D

ai /

Inte

rnat

ion

al J

ou

rnal

of

Co

al G

eo

logy

94

(2

01

2) 6

7–9

3

Page 12: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Ad

vant

ages

Reu

ses

a w

aste

pro

du

ct◦

Co

al w

ill b

e an

imp

ort

ant

ener

gy s

ou

rce

for

dec

ades

◦W

orl

dw

ide

sco

pe

No

exc

avat

ion

, ben

efic

iati

on

, an

d m

illin

g re

qu

ired

◦Id

eal f

orm

fo

r ch

emic

al p

roce

ssin

g

◦El

imin

ates

a m

ajo

r p

art

of

the

co

st a

nd

en

viro

nm

enta

l im

pac

t o

f R

EE p

rod

uct

ion

Nee

d f

or

add

itio

nal

min

es le

ss u

rgen

t◦

Tho

riu

m a

sso

ciat

ed w

ith

co

nve

nti

on

al o

res

12

Page 13: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Dis

adva

ntag

esR

EE s

epar

atio

n a

nd

pu

rifi

cati

on

sti

ll d

iffi

cult

◦En

ergy

an

d c

hem

ical

inte

nsi

ve

◦B

ased

larg

ely

in C

hin

a

Co

al a

sh h

as m

uch

low

er R

EE c

on

ten

t th

an

con

cen

trat

ed o

re

Met

als

entr

ain

ed w

ith

in a

sh p

arti

cles

Ash

co

mp

osi

tio

n h

eavi

ly d

epen

den

t o

n c

oal

ge

olo

gy

13

Page 14: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Res

earc

h O

bje

ctiv

es1

.C

har

acte

rize

REE

co

nte

nt

of

Am

eric

an f

ly a

shes

an

d c

orr

elat

e w

ith

ash

att

rib

ute

s

2.

Inve

stig

ate

stru

ctu

re a

nd

loca

tio

n o

f R

EE w

ith

in

fly

ash

usi

ng

seq

uen

tial

ext

ract

ion

s an

d X

AS

3.

Test

ind

ust

rial

ly-r

elev

ant

extr

acti

on

met

ho

ds,

q

uan

tify

ext

ract

able

REE

, an

d m

easu

re r

esid

ual

tr

ace

elem

ents

in f

ly a

sh a

fter

ext

ract

ion

14

Page 15: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Res

earc

h O

bje

ctiv

es1

.C

har

acte

rize

REE

co

nte

nt

of

Am

eri

can

fly

ash

es

and

co

rre

late

wit

h a

sh a

ttri

bu

tes

2.

Inve

stig

ate

stru

ctu

re a

nd

loca

tio

n o

f R

EE w

ith

in

fly

ash

usi

ng

seq

uen

tial

ext

ract

ion

s an

d X

AS

3.

Test

ind

ust

rial

ly-r

elev

ant

extr

acti

on

met

ho

ds,

q

uan

tify

ext

ract

able

REE

, an

d m

easu

re r

esid

ual

tr

ace

elem

ents

in f

ly a

sh a

fter

ext

ract

ion

15

Page 16: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Hyp

oth

eses

A.

Ap

pal

ach

ian

Bas

in c

oal

ash

es w

ill h

ave

hig

her

R

EE c

on

ten

t th

an Il

lino

is B

asin

or

Pow

der

Riv

er

Bas

in a

shes

.

B.

Na 2

O2

sin

teri

ng

will

be

as e

ffec

tive

as

HF

dig

esti

on

fo

r q

uan

tify

ing

REE

in f

ly a

sh. F

or

oth

er

elem

ents

, HF

dig

esti

on

will

be

mo

re a

ccu

rate

.

C.

REE

co

nte

nt

will

be

corr

elat

ed w

ith

BET

su

rfac

e ar

ea, p

arti

cle

size

, an

d m

ajo

r o

xid

e co

nte

nt.

16

Page 17: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Ash

Ch

arac

teri

zati

on

ALK

ALI

NE

SIN

TER

ING

Bak

e sa

mp

le in

Zr

cru

cib

le

wit

h s

od

ium

per

oxi

de

Leac

h w

ith

nit

ric

acid

USG

S m

eth

od

fo

r R

EE

anal

ysis

HF/

HN

O3

DIG

ESTI

ON

Wh

ole

ro

ck d

iges

tio

n

Evap

ora

te H

F an

d r

e-d

isso

lve

in n

itri

c ac

id

Qu

anti

fica

tio

n o

f m

etal

s re

mai

nin

g af

ter

extr

acti

on

17

Test

ch

arac

teri

zati

on

met

ho

ds

usi

ng

NIS

T SR

M

16

33

c as

a s

tan

dar

d

Det

erm

ine

REE

co

nce

ntr

atio

n in

co

al a

sh s

amp

les

Page 18: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Oth

er P

aram

eter

sO

bje

ctiv

e 1

:C

orr

elat

e as

h c

har

acte

rist

ics

wit

h t

ota

l an

d e

xtra

ctab

le R

EE d

ata

BET

su

rfac

e ar

ea◦

Mea

sure

gas

ad

sorp

tio

n

◦M

ore

po

rou

s fl

y as

h m

ay h

ave

hig

her

ext

ract

able

REE

co

nte

nt

rega

rdle

ss o

f p

arti

cle

size

An

alys

es a

lrea

dy

per

form

ed b

y C

AER

:◦

Maj

or

oxi

de

co

nte

nt

◦M

iner

alo

gy

◦A

sh c

on

ten

t o

f so

urc

e c

oal

18

Page 19: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Prel

imin

ary

Res

ult

s1

.H

F d

iges

tio

n a

nd

Na 2

O2

sin

teri

ng

are

accu

rate

q

uan

tifi

cati

on

met

ho

ds

2.

Man

y fl

y as

hes

co

nta

in 5

00

-60

0 p

pm

REE

3.

Cle

ar c

lust

erin

g b

y co

al b

asin

; Ap

pal

ach

ian

B

asin

ash

es s

eem

mo

st p

rom

isin

g

No

te: A

dd

itio

nal

ash

sam

ple

s w

ill b

e co

llect

ed

fro

m p

lan

ts in

th

e C

aro

linas

19

Page 20: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Prio

riti

zin

g A

shes

Co

al a

shes

co

mp

are

favo

rab

ly w

ith

REE

o

re d

epo

sits

20

V.V

. Ser

edin

, S. D

ai /

Inte

rnat

ion

al J

ou

rnal

of

Co

al G

eo

logy

94

(2

01

2) 6

7–9

3

Page 21: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Res

earc

h O

bje

ctiv

es1

.C

har

acte

rize

REE

co

nte

nt

of

Am

eric

an f

ly a

shes

an

d c

orr

elat

e w

ith

ash

att

rib

ute

s

2.

Inve

stig

ate

str

uct

ure

an

d lo

cati

on

of

REE

wit

hin

fl

y as

h u

sin

g se

qu

en

tial

ext

ract

ion

s an

d X

AS

3.

Test

ind

ust

rial

ly-r

elev

ant

extr

acti

on

met

ho

ds,

q

uan

tify

ext

ract

able

REE

, an

d m

easu

re r

esid

ual

tr

ace

elem

ents

in f

ly a

sh a

fter

ext

ract

ion

21

Page 22: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Hyp

oth

eses

D.

REE

will

be

entr

ain

ed in

th

e gl

assy

mat

rix

of

the

fly

ash

par

ticl

es r

ath

er t

han

su

rfac

e-b

ou

nd

. Th

e m

ajo

rity

of

the

REE

will

be

pre

sen

t in

th

e H

F-le

ach

able

fra

ctio

n o

f th

e as

h (

i.e. s

ilica

tes)

.

E.Th

e m

iner

al p

has

e o

f th

e ra

re e

arth

ele

men

ts in

fl

y as

h w

ill d

eter

min

e h

ow

eas

ily t

hey

can

be

extr

acte

d a

nd

wh

ich

aci

d is

mo

st e

ffec

tive

.

22

Page 23: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Seq

uen

tial

Ext

ract

ion

s4

g a

sh s

amp

le, 2

0 m

L o

f ex

trac

tan

t, 1

5 h

ou

rs

1.

Dei

on

ized

wat

er (

wat

er s

olu

ble

fra

ctio

n)

2.

1 M

am

mo

niu

m a

ceta

te (

ion

exc

han

geab

le)

3.

3 M

HC

l(ca

rbo

nat

e-b

ou

nd

)

4.

8.8

M H

2O

2an

d 4

M H

NO

3(o

xid

izab

le)

5.

1:1

mix

ture

of

HF

and

HN

O3

(sili

cate

-bo

un

d)

23

Ad

apte

d f

rom

Hu

ggin

s et

al.,

20

00

/ M

od

es o

f o

ccu

rren

ce o

f C

r in

fo

ur

US

coal

s

Page 24: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

24

Yuan

, 20

09

/ L

each

ing

char

acte

rist

ics

of

met

als

in f

ly a

sh

Page 25: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

X-ra

y M

eth

od

s

XA

NES

Nea

r-ed

ge (

±50

eV

)

Thre

e-d

imen

sio

nal

geo

met

ry

Co

ord

inat

ion

en

viro

nm

ent

Oxi

dat

ion

sta

te

EXA

FS

Exte

nd

ed

fin

e st

ruct

ure

(1

00

-10

00

eV

bey

on

d e

dge

)

Co

ord

inat

ion

en

viro

nm

ent

Nea

rest

nei

ghb

ori

ng

ato

ms

25

X-r

ay A

bso

rpti

on

Sp

ectr

osc

op

y (X

AS)

Req

uir

es s

ynch

rotr

on

rad

iati

on

so

urc

e

Page 26: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

26

Par

son

s et

al.,

20

02

/ E

nvi

ron

men

tal a

nd

Bio

logi

cal A

pp

licat

ion

s o

f EX

AFS

an

d X

AN

ES S

pec

tro

sco

pie

s

Page 27: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Inte

rfer

ence

sA

bso

rpti

on

ed

ges

of

oth

er e

lem

ents

in s

amp

le m

ay

lie in

XA

NES

/EX

AFS

reg

ion

27

Bin

din

g e

ner

gy

(eV

)E

mis

sio

n (

eV)

No

.E

lem

.K

-ed

ge

LII

I-ed

ge

Kα1

Lα1

22

Ti

4966

4510.8

4504.9

23

V5465

4952.2

24

Cr

5989

5414.7

25

Mn

6539

5898.8

39

Y1

70

38

14

95

8.4

55

Cs

35985

5012

4619.8

56

Ba

37441

5247

4466.3

4827.5

57

La

38

92

55

48

33

34

41

.84

65

1.0

58

Ce

40

44

35

73

23

47

19

.74

84

0.2

60

Nd

43

56

96

20

83

73

61

.05

23

0.4

92

U17166

13614

Hu

ggin

s et

al.,

20

00

/ M

od

es o

f o

ccu

rren

ce o

f C

r in

fo

ur

US

coal

s

Page 28: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Yttr

ium

XA

SM

ost

pro

mis

ing

REE

◦Se

con

d m

ost

ab

un

dan

t (u

p t

o 1

00

mg

/kg)

◦N

o n

ota

ble

inte

rfer

ence

s

◦C

riti

cal R

EE

Ref

eren

ce m

ater

ials

sh

ou

ld m

imic

fly

ash

sam

ple

s (e

.g. y

ttri

um

min

eral

s em

bed

ded

in g

lass

)

Ob

ject

ive

2re

sult

s w

ill in

flu

ence

ext

ract

ion

m

eth

od

sel

ecti

on

in O

bje

ctiv

e 3

28

Go

od

arzi

and

Hu

ggin

s, 2

00

1 /

Sp

ecie

s o

f A

s, C

r, a

nd

Ni i

n m

illed

co

al, b

ott

om

ash

, an

d f

ly a

sh f

rom

a p

ow

er p

lan

t in

we

ster

n C

anad

a

Page 29: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Res

earc

h O

bje

ctiv

es1

.C

har

acte

rize

REE

co

nte

nt

of

Am

eric

an f

ly a

shes

an

d c

orr

elat

e w

ith

ash

att

rib

ute

s

2.

Inve

stig

ate

stru

ctu

re a

nd

loca

tio

n o

f R

EE w

ith

in

fly

ash

usi

ng

seq

uen

tial

ext

ract

ion

s an

d X

AS

3.

Test

ind

ust

rial

ly-r

ele

van

t ex

trac

tio

n m

eth

od

s,

qu

anti

fy e

xtra

ctab

le R

EE, a

nd

me

asu

re r

esi

du

al

trac

e e

lem

en

ts in

fly

ash

aft

er

extr

acti

on

29

Page 30: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Hyp

oth

eses

F.So

nic

atio

n o

r si

nte

rin

g o

f sa

mp

les

pri

or

to a

cid

d

iges

tio

n w

ill im

pro

ve R

EE r

eco

very

an

d e

nab

le

the

use

of

mo

re d

ilute

aci

ds.

G.

Rec

ove

rin

g R

EE f

rom

fly

ash

will

sim

ult

aneo

usl

y re

mo

ve t

he

maj

ori

ty o

f th

e le

ach

able

to

xic

elem

ents

(e.

g. A

s, S

e, C

r, P

b).

30

Page 31: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Init

ial M

eth

od

sD

irec

t A

cid

Lea

chin

g◦

8 M

HC

lat

10

5°C

for

2 h

ou

rs

Pre

ssu

re-D

iges

tio

n A

cid

Lea

ch◦

Pre

-tre

at w

ith

NaO

Hso

luti

on

at

20

0-2

45

°C

◦A

mb

ien

t te

mp

erat

ure

leac

h w

ith

12

.5 M

HC

l

Sulf

uri

c A

cid

Lea

chin

g◦

10

% v

/v H

2SO

4at

30

-80

°C f

or

2 h

ou

rs

◦Sp

ecif

ical

ly f

or

REE

in f

ly a

sh

31

Page 32: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Extr

acti

on

Var

iab

les

1.

Tem

per

atu

re (

25

-20

0°C

)

2.

Solid

-to

-liq

uid

rat

io (

up

to

1:2

)

3.

Aci

d t

ype

and

co

nce

ntr

atio

n

4.

Pre

trea

tmen

ts (

e.g.

sin

teri

ng)

5.

Du

rati

on

(3

0 m

inu

tes

to o

vern

igh

t)

32

Page 33: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Sint

erin

gC

on

vert

s m

iner

als

to a

cid

so

lub

le f

orm

s

Allo

ws

leac

hin

g w

ith

dilu

te a

cid

◦2

5%

HN

O3

afte

r si

nte

rin

g (O

bje

ctiv

e 1

)

◦Tw

ice

as e

ffec

tive

as

con

cen

trat

ed H

NO

3al

on

e

Var

iab

les

to b

e te

sted

:◦

CaO

and

FG

D w

aste

inst

ead

of

Na 2

O2

◦R

atio

of

flu

x to

sam

ple

◦Le

ach

ing

acid

an

d c

on

cen

trat

ion

33

Page 34: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Post

-Ext

ract

ion

Qu

anti

fy R

EE a

nd

tra

ce e

lem

ents

in r

emai

nin

g so

lids

◦Ev

apo

rate

aci

d

◦H

F d

iges

tio

n (

Ob

ject

ive

1)

Cal

cula

te e

xtra

ctio

n e

ffic

ien

cies

by

met

ho

d

Co

rrel

ate

ash

par

amet

ers

(Ob

ject

ive

1)

wit

h

extr

acti

on

eff

icie

ncy

34

Page 35: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Prel

imin

ary

Res

ult

sH

Cli

s th

e m

ost

eff

ecti

ve a

cid

Effe

cts

of

acid

an

d s

on

icat

ion

var

y co

nsi

der

ably

b

etw

een

sam

ple

s◦

May

dep

end

on

ash

ch

arac

teri

stic

s (O

bje

ctiv

e 1

)

◦H

igh

to

tal R

EE d

oes

no

t im

ply

hig

h e

xtra

ctab

le R

EE

Son

icat

ion

ap

pea

rs t

o h

ind

er R

EE r

eco

very

in

man

y ca

ses

(HC

lan

d H

NO

3)

◦In

con

sist

ent

resu

lts

for

H2SO

4

35

Page 36: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Prel

imin

ary

Res

ult

sH

Cli

s th

e m

ost

eff

ecti

ve a

cid

Effe

cts

of

acid

an

d s

on

icat

ion

var

y co

nsi

der

ably

b

etw

een

sam

ple

s◦

May

dep

end

on

ash

ch

arac

teri

stic

s (O

bje

ctiv

e 1

)

◦H

igh

to

tal R

EE d

oes

no

t im

ply

hig

h e

xtra

ctab

le R

EE

Son

icat

ion

ap

pea

rs t

o h

ind

er R

EE r

eco

very

in

man

y ca

ses

(HC

lan

d H

NO

3)

◦In

con

sist

ent

resu

lts

for

H2SO

4

36

Page 37: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Inte

llect

ual

Mer

itO

bje

ctiv

e 1

◦R

EE t

ota

ls f

or

bro

ad s

amp

le o

f A

mer

ican

fly

ash

es◦

Ash

par

amet

ers

linke

d t

o t

ota

l/ex

trac

tab

le R

EE

Ob

ject

ive

2◦

Use

of

XA

S to

exa

min

e R

EE in

fly

ash

◦B

ette

r u

nd

erst

and

ing

of

REE

str

uct

ure

in f

ly a

sh

Ob

ject

ive

3◦

Ap

plic

atio

n o

f re

leva

nt

extr

acti

on

met

ho

ds

to R

EE in

fl

y as

h

37

Page 38: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Bro

ader

Imp

acts

Envi

ron

men

tal

◦B

enef

icia

l reu

se o

f fl

y as

h◦

Red

uct

ion

in t

oxi

c tr

ace

elem

ents

Eco

no

mic

◦W

aste

mo

net

izat

ion

◦A

lter

nat

ive

sou

rce

for

cru

cial

REE

Nat

ion

al S

ecu

rity

◦St

able

do

mes

tic

sup

ply

of

stra

tegi

c m

etal

s◦

Co

nsi

der

ed c

riti

cal e

lem

ents

by

DO

E

38

Page 39: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Co

ncl

usi

on

Fly

ash

is a

pro

mis

ing

alte

rnat

ive

sou

rce

of

REE

Stro

ng

nee

d f

or

furt

her

res

earc

h o

n f

ly a

sh R

EE

con

ten

t, s

tru

ctu

re, a

nd

ext

ract

ion

Up

com

ing

wo

rk◦

Co

llect

ad

dit

ion

al a

sh s

amp

les

fro

m D

uke

En

ergy

an

d S

ante

e C

oo

per

◦B

egin

acq

uir

ing

XA

S st

and

ard

s

◦Se

qu

enti

al e

xtra

ctio

ns

39

Page 40: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Ack

no

wle

dge

men

tsTh

e H

su-K

im la

b

Dr.

Jam

es

C. H

ow

er

Dr.

Gar

y S.

Dw

yer

Osm

an U

lug

40

Page 41: Recovering Rare Earth Metals from Coal Fly AshRecovering Rare Earth Metals from Coal Fly Ash Author: Taggart, Ross K Subject: 2015 World of Coal Ash (WOCA) Conference in Nasvhille,

Ref

eren

ces

Lon

g, K

.R.,

20

11

, Th

e fu

ture

of

rare

ear

th e

lem

ents

; w

ill t

hes

e h

igh

-tec

h

ind

ust

ry e

lem

ents

co

nti

nu

e in

sh

ort

su

pp

ly?:

U.S

. Geo

logi

cal S

urv

ey

Op

en-F

ile R

epo

rt 2

01

1-1

18

9, 4

1 p

. [h

ttp

://p

ub

s.u

sgs.

go

v/o

f/2

01

1/1

18

9/]

.

Sch

wei

nfu

rth

, S.P

., 2

00

9, A

n in

tro

du

ctio

n t

o c

oal

qu

alit

y, in

Pie

rce,

B.S

.,

and

Den

nen

, K.O

., e

ds.

, Th

e N

atio

nal

Co

al R

eso

urc

e A

sses

smen

t O

verv

iew

: U.S

. Geo

logi

cal S

urv

ey P

rofe

ssio

nal

Pap

er 1

62

5–F

, C

hap

ter

C, 1

6 p

.

V.V.

Ser

edin

, S. D

ai /

Inte

rnat

ion

al J

ou

rnal

of

Co

al G

eolo

gy 9

4 (

20

12

) 6

7–

93

41