Extraction of Colstrip coal using supersolvents in conjunction with the water-gas shift reaction
by Sylvester John Losinski
A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science in
Chemical Engineering
Montana State University
© Copyright by Sylvester John Losinski (1986)
Abstract:
Coal extraction using supersolvents, tetramethylurea (TMU) and hexamethylphosphoramide (HMPA),
in the presence of the water-gas shift reaction may be a viable method for hydrogenating and extracting
coal products in one operation. In this investigation the effects of solvent mixture, solvent pH,
temperature, and carbon monoxide pressure on coal extraction were evaluated. Experiments were
conducted on Colstrip sub-bituminous coal and other coals in a magnetically stirred batch autoclave
with carbon monoxide pressures ranging from 250 to 1000 psig.
Extraction of Colstrip coal to 35 percent was observed at 1607deg;C using a solvent mixture of
TMU/HMPA/Tetralin/H2O with a pH of 13.12 and a carbon monoxide pressure of 500 psig.
It was found that extraction decreased with increasing carbon monoxide pressure in the range of 250 to
1000 psig, but the extraction value for any pressure was greater than when carbon monoxide was not
used.
Extraction by the present procedure was not found to be temperature dependent over the range of 25 to
200°C. Possible explanations for this unexpected result have been presented.
Solvent was retained in the extraction residue in the amount of 6 to 17 percent by weight. The total
extraction must be dramatically increased, or the amount of solvent retention decreased, for the process
to be viable as a coal extraction method. EXTRACTION OF COLSTRIP COAL USING
SUPERSOLVENTS IN CONJUNCTION WITH
THE WATER-GAS SHIFT REACTION
by
S y l v e s t e r John L o s i n s k i
A t h e s i s s u b m itte d in p a r t i a l f u l f i l l m e n t
o f th e r e q u ir e m e n ts f o r th e degree
of
Master o f
Science
in
Chemi cal
E ngineering
MONTANA STATE UNIVERSITY
Bozeman, Mont ana
March I 986
M372
Uf. Sy
ii
Approval
of
a th e sis
S ylvester
subm itted
by
John L o s i n s k i
T h i s t h e s i s has been r ead by ea ch member o f t h e a u t h o r ' s g r a d u a t e
c o m m i t t e e and has been f o u n d t o be s a t i s f a c t o r y
regarding
content,
E n g l i s h u s a g e , f o r m a t , c i t a t i o n s , b i b l i o g r a p h i c s t y l e , and c o n s i s t e n c y ,
and i s r e a d y f o r s u b m i s s i o n t o t h e C o l l e g e o f G r a d u a t e S t u d i e s .
-------------------
'
Approved f o r
/}/IaSbcA s
C h a i r p e r s o n , G ra d u a te Committee
th e M a jo r Department
Xg
Dat e
Approved f o r
Dat e
the C o lle g e o f
Graduate S tu d ie s
G r a d u a t e Dean
STATEMENT OF PERMISSION TO USE
In p r e s e n t i n g
requirem ents
that
shall
provided
Perm ission
m ate ria l
in
my w r i t t e n
Si g n a t u r e
Dat e
th is
from t h i s
fo r
from o r
paper f o r
perm ission.
purposes.
fin a n c ia l
ru le s o f the
or
gain
source
special
i s made.
reproduction o f
in h i s absence,
the o p in io n o f e i t h e r ,
s c h o la rly
I agree
paper a re a llo w a b le w it h o u t
by my m a j o r p r o f e s s o r ,
in
the
to borrowers under
t h a t a c c u r a t e acknowledgement o f
L i b r a r i e s w hen,
is
fu lfillm e n t of
d e g r e e a t Mont ana S t a t e U n i v e r s i t y ,
fo r extensive q uotatio n
p a p e r may be g r a n t e d
the m a te ria l
in p a r t i a l
make . i t a v a i l a b l e
B r ie f q u o ta tio n s
perm ission,
Dean o f
th e sis
f o r a m a ste r's
the L ib r a r y
L ib ra ry.
th is
th is
by t h e
t h e p r o p o s e d use o f
Any c o p y i n g o r us e o f t h e
shall
n o t be a l l o w e d w i t h o u t
ACKNOWLEDGEMENTS
The a u t h o r
the
th e ir
C hem ic al
expresses
E ngineering
h e l p and g u i d a n c e .
S e ar s f o r
Co-workers
special
his
I.
his
appreciatio n
Department
A special
th a n k you.
Tsao,
Turgut
the
S ahin,
th e
Mont ana
t h a n k you
h e l p and s u p p o r t d u r i n g
Hsing
at
to
State
is extended
course
and
fa c u lty
of
Ti m
th is
Ward
and
s ta ff
U n ive rsity
t o Dr.
of
fo r
John T .
in v e s tig a tio n .
a lso
deserve
a
V
TABLE OF CONTENTS
Page
1.
APPROVAL.......................................................................................................
2.
STATEMENT OF PERMISSION TO USE..........................................................................
3.
ACKNOWLEDGEMENTS. ..........................................................................................................
4.
TABLE OF CONTENTS.........................................................................................
,5.
L IST OF TABLES......................
6.
L I S T OF FIGURES............................................................................................................... v i i I
7.
ABSTRACT............................................................ ..................................................................
8.
INTRODUCTION......................................................................................................................
I
Coal S t r u c t u r e ..........................................................................................................
S o l v e n t T h e o r y ..........................................................................
TMU and HMPA.....................................................................................
W a t e r - G a s S h i f t R e a c t i o n ..................................................................................
R e l a t e d W o r k ..............................................................................
R e s e a r c h O b j e c t i v e ................................................................................................
3
4
9.
EXPERIMENTAL...................
Raw M a t e r i a l s and C hem ic al R e a g e n t s ........................................................
E x p e r i m e n t a l A p p a r a t u s .......................................................................................
E x p e r i m e n t a l P r o c e d u r e .......................................................................................
A n a l y t i c a l P r o c e d u r e .........................................................
10.
RESULTS AND DISCUSSION........................
C a l c u l a t i o n s and A s s u m p t i o n s ............ ,..........................................................
E r r o r and R e l i a b i l i t y o f M e a s u r e m e n t s ...................................................
The Coal D r y i n g A n o m a l y ....................................................................................
T e m p e r a t u r e E f f e c t s ..............................................................................................
P r e s s u r e E f f e c t s .....................................................................................................
pH E f f e c t s ........................................................................ '..........................................
Coal Rank E f f e c t s ...................................................................................................
S o l v e n t R e t e n t i o n ...................................................................................................
A d d i t i o n a l E x p e r i m e n t a t i o n .................................
i'
' ''
'V
v
v ii
6
9
11
15
16
16
17
21
22
24
24
28
29
30
33
36
40
42
44
vi
TABLE OF CONTENTS--C o n t i n u e d
Page
11.
SUMMARY AND CONCLUSIONS............................................................................................
2t7
12.
RECOMMENDATIONS FOR FUTURE RESEARCH.............................................................
^9
13.
REFERENCES CITED.............................................................................................................
50
14.
APPENDICES...........................................................................................................................
54
Appendix
Appendix
Appendix
Appendix
Appendix
A— Raw Data f r o m E x t r a c t i o n E x p e r i m e n t s ........................
B - - S a m p l e C a l c u l a t i o n ....................................................................
C— R e s u l t s o f E x t r a c t i o n R u n s .................................................
D - - E r r o r A n a l y s i s .............................................................................
E - - llW a t e r n Loss J u s t i f i c a t i o n ................................................
55
51
65
67
72
vi i
L IS T OF' TABLES
Tables
.
Page
1.
Physical
P roperties
2.
C he m i c a l
R ea ge n ts U s e d . . . . ; . . ..........................
3.
S p e c ific a tio n s
o f TMU and HMPA............................................................
o f M agn e tica lly S tir r e d
7
17
R e a c t o r ....................................
20
E r r o r o f M e a s u r e m e n t s ........................................................................
28
4.
R e la tive
5.
E l e m e n t a l . A n a l y s t s f o r Wet and D ry C o a l . . ......................................... ; .
29
6.
Gram Mol e E l e m e n t a l
30
7.
E xtra ctio n
8.
Experim ental
C onditions
9.
Raw Data f o r
Experimental
R esults
L o s s ...........................................
fo r
A nalysis o f
In d ivid u a lize d
fo r
Coal
E x p e r i m e n t s ...........................
Each R e a c t i o n
Run.....................................
56
R un s ..............................................
58
E x p e r i m e n t a t i o n ...........................
60
E xtra ctio n
Used
in
45
10.
Ch em ic al
11.
A b s o l u t e E x t r a c t i o n V a l u e s and S o l v e n t R e t e n t i o n
f o r Each E x p e r i m e n t a l R u n . . . . . . .......................................
66
vi i i
LI ST OF FIGURES
Figures
Page
1.
S h i n n ' s Model
of
Bi Lumi nous Coal
S t r u c t u r e .........................................
5
2.
S t r u c t u r e o f TMU and HMPA..................................................................................
7
3.
P r o p os e d Mechani sm o f Aqueous A l k a l i C a t a l y z e d
W a t e r - G a s S h i f t C o n v e r s i o n ...................................................................................
10
4.
M ag n e tica lly
5.
Flow Diagram f o r
6.
T e m p e r a t u r e Dependence o f
7.
P r e s s u r e Dependence o f
8.
9.
S tirre d
R e a c t o r ...........................................................................
Experim ental
R e a c t o r .................................................. *
E x t r a c t i o n ...........................................
E x t r a c t i o n ................................................................
18
19
32
34
pH o f S o l v e n t B e f o r e R e a c t i o n V e r s u s O bs er ved
E x t r a c t i o n .........................................................................................
pH o f S o l v e n t A f t e r R e a c t i o n V e r s u s O bs er ved
E x t r a c t i o n .........................................................................................................................
10.
I n i t i a l Carbon C o n t e n t V e r s u s O bs er v ed
E x t r a c t i o n ...........................................................................
11.
Solvent
R etention
V e r s u s E x t r a c t i o n ..........................
37
38
43
ABSTRACT
Coal:
e xtra ctio n
using
su p e rs o l v e n t s , t e t r a m e t h y I u rea
(TMU)
and
h e x a m e t h y l p h o s p h o r a m i d e (HMPA), i n t h e p r e s e n c e o f t h e w a t e r - g a s s h i f t
r e a c t i o n may be a v i a b l e met hod f o r h y d r o g e n a t i n g and e x t r a c t i n g c o a l
p r o d u c t s i n one o p e r a t i o n .
In t h i s i n v e s t i g a t i o n t h e e f f e c t s o f s o l v e n t
m i x t u r e , s o l v e n t pH, t e m p e r a t u r e , and c a r b o n m o n o x i d e p r e s s u r e on c o a l
e xtra ctio n
were e v a l u a t e d .
E x perim ents were conducte d
on
C o ls trip
s u b -b itu m in o u s coal
and o t h e r c o a l s
in a m a g n e t i c a l l y s t i r r e d batch
a u t o c l a v e w i t h c a r b o n m o n o x i d e p r e s s u r e s r a n g i n g f r o m 250 t o 1000 p s i g .
E x t r a c t i o n o f C o l s t r i p c o a l t o 35 p e r c e n t was
u s i n g a s o l v e n t m i x t u r e o f T M U / H M P A / T e t r a l i n / H 20 w i t h
a c a r b o n m o n o x i d e p r e s s u r e o f 500 p s i g .
o b s e r v e d a t 160 C
a pH o f 13- 12 and
I t was f o u n d
that
e xtra ctio n
decreased w it h
increasing
carbon
m o n o x i d e p r e s s u r e i n t h e r a n g e o f 250 t o 1000 p s i g , b u t t h e e x t r a c t i o n
v a l u e f o r a ny p r e s s u r e was g r e a t e r t h a n when c a r b o n m o n o x i d e was n o t
used.
E x t r a c t i o n by t h e p r e s e n t p r o c e d u r e was n o t f o u n d t o be t e m p e r a t u r e
d e p e n d e n t o v e r t h e r a n g e o f 25 t o 2 0 0 ° C.
Possible e x p la n a tio n s fo r t h is
u n e x p e c t e d r e s u l t have been p r e s e n t e d .
S o l v e n t was r e t a i n e d i n t h e e x t r a c t i o n r e s i d u e i n t h e amount o f 6
t o 17 p e r c e n t by w e i g h t .
The t o t a l
e x t r a c t i o n mus t be d r a m a t i c a l l y
i n c r e a s e d , o r t h e amount o f s o l v e n t r e t e n t i o n d e c r e a s e d , f o r t h e p r o c e s s
t o be v i a b l e as a c o a l e x t r a c t i o n m e t h o d .
INTRODUCTION
coal
In
S ear s
(I)
has
using
a sp e c ific
p re lim in a ry
able
to
suggeste d
group o f
experim ents,
show t h a t
unusually
co a l.
Based
re la te d
high
e xtra c tio n
e xtra ctio n
th is
Energy
supersolvents.
and
pressure,
he
was
for
c e rta in
ty pes
of
a
proposal
to
the
form ula
to
c h a ra c te ris tic s
evidence
in ve stig a te
process
fo r
has p r o v i d e d
the
he
subm itted
the
fe a s ib ility
liq u e fa c tio n
the fu n ding
fo r
th is
of
of
using
co a l.
a
super­
The e n s u i n g
in v e s tig a tio n
and o t h e r
work.
of
supersolvents
on
the blendin g o f
coal
tem perature
of
,
upon
e ffe ctive n e ss
that
residue.
T.
Ward
(2)
tetram ethyIurea ,
the
e xtra ctio n
supersol vents
be o b t a i n e d
d oc ument
liq u e fa c tio n
M = C,P,S
C o-in ve stig a to rs
could
the
he c a l l e d
\
R
e x h ib it
research g ra n t
room
that
to
/
1
R
solvent
chem icals
the ge n e ra l
R— M— N
of
approach
R
Il
Department
novel
at
solvents o f
0
a
of
and
C.
Ichioka
co a l.
re su lte d
large
exami ned
hexamet h y I p h o s p h o r a m i d e ,
in
Their
amount s
of
e ffo rts
b etter e x tra c tio n
by any one s u p e r s o l v e n t a l o n e .
re la tiv e ly
( 3)
solvent
and
the
other
revealed
that
o f coal
than
They w e r e a l s o a b l e
were
retained
in
to
the
2
I.
S a h in , another c o - in v e s tig a to r ,
a packed
mine
of
if
bed
reactor
e nhan ced
coal
in
the
m a te ria ls
w ith
e xtra ctio n
presence
handling
te n ta tiv e ly
enhancing
and
conclude
overpressure
o f supersolven ts.
His e f f o r t s
sw elling
hydrogen
formed
hav e
in
d oc um e n te d
the w a te r-g a s
t h e w a t e i — gas
s h ift
tio n .
process
th e coal
could
technology.
in
would
in
that
when
et
aI .
( 8)
both
The mos t
by
was
in
to d e te r­
hydrogenation
were th w a rte d
by
he
able
to
in e ffe c tiv e
in
was
a
the
re a c tiv ity
re a ctio n
o f coal
w ith
and
the
S ear s
by u s i n g
supersolvent
advantage
e x tra c tio n
of
(4,5,6).
may be p o s s i b l e
d is tin c t
extrac
over
other
hydrogenation
of
i n one o p e r a t i o n .
a
new
im p o rta n t o f
several
or
factors
improved
these f a c t o r s
a
hydrogen u t i l i z a t i o n
a
s o lv e n t overhydrogenation
A
generation o f hydrogen-rich f i n a l
a
ease o f s o l i d s
A
reduction of
A
r e d u c t i o n o f p rocess t e m p e r a t u r e
P relim inary
e ffo rt
but
high
s h ift
id e n tifie d
e va lu a tin g
the
co n ju n ctio n
have
be a c c o m p l i s h e d
W hitehurst
considered
rea ctio n
processes
experim ents
o f co a l.
t h a t e nhan ced e x t r a c t i o n
e xtra ctio n
problems,
overpressure
(7) p o s tu la te d
This
an
be a c h i e v e d
that
coal
in
could
in v e s tig a to rs
n a s c e n t hydrogen
of
coal
the e x t r a c t io n
Other
hydrogen
performed several
that
should
be
c o a l - I i q u e f a c t ion
are:
e ffic ie n c y
p r o du ct s
separations
reaction
experim ental
work
s u p e r s o l v e n t c o a l - I i q u e f a c t ion
t ime
performed
by
S ear s
p r o c e s s may have
(I)
in d ic a te s
s ig n ific a n t
that
the
advanta ges
3
over
e x is tin g
c o a l - I i q u e f a c t ion
fie d
by W h i t e h u r s t .
The p u r p o s e o f
coal
using
th is
in v e s tig a tio n
supersolvents
re a c tio n .
The
processes
e ffe cts
in
of
p la n t
deposits
m atter
process
carbon
over
d ioxide
lig n ite ,
tim escale
e x c e lle n t
o f coal
( 9 , 1 0 , 11 ) .
It
has
complex.
macerals o r
m atter,
The
been
but
m atter
m olecule.
of
oxygen,
to
coals
is
firs t
bitum inous,
Several
exam ination
as
of
s h ift
tem perature,
of
coal
Each
lith o ty p e
contain
(9).
peat
and
of
persons
coal
has
have
fu n ctio n a l
The s t r u c t u r e
fo r.a
been
proposed
groups,
to
fin a lly
on
the
the
form
o rig in
reveals
of
and
then
a
to
coal.
form ation
coal
that
of
On
a n th ra c ite
nature
on
coal i f ic a t io n
rank
e x h ib its
high q u a n t i t i e s
the
higher
several
Iith o typ e s
and h e a t
in
of
and
a m ixtu re o f
the
pressure
converted
is
Some o f
observed
e x tra c tio n
p rim a rily
m orphological
that
makeup
id e n ti­
water-gas
s uc h
During
the
w h ile others
experim ental Iy
tim e.
found
p ro p e rtie s.
the
the
of
a v a ila b le
Iith o ty p e s .
(12,13,14) .
a ctio n
are
instead
c h em ic al ,
the
references
M icroscopic
homogen eous ,
chemical
p la n t
w ith
parameters
of
leads
sub-bitum inous,
Several
by
periods
w a te r,
examine
fa cto rs
S tructure
e lim in a tio n
and
the
t h e s o l v e n t w e r e t o be c h a r a c t e r i z e d .
formed
long
progressive
geolog ic
coal
were
to
conju n ctio n
Coal
Coal
was
rea ctio n
p r e s s u r e , s o l v e n t , and pH o f
based on
it
is
very
is
not
d iffe re n t
id e n tifia b le
d iffe re n t
physical
are p r i m a r i l y
and
in e r t m ineral
o f e x tra c ta b le m a te ria l.
studied
by
many
structures,
that
bitum inous
portray
coal
s c ie n tis ts
in co rp o ra tin g
an
proposed
"average"
by S h i n n
4
( 1 5)
is
shown
coal
is
a
in
Figure
h ig h ly
to
low
is
tie d
it
is
fu n ctio n a l
up i n
s e v e rity
weak bonds
in
be
groups.
the a ro m a tic
coal
that
can
seen
arom atic
liq u e fa c tio n
the
thought
As
c r o s s I inked
oxygen-con taining
m olecule
I.
Most
of
model
the
a
There
p rim a rily
reactions
la rg e
is
are
ester
are
structure,
n itro g e n
and as such
re a ctio n s.
liq u e fa c tio n
the
compound w i t h
rin g s
stru ctu re ,
from
in
the
probably
several
and
number o f
at
explain
the
immune
re la tiv e ly
ether
in itia te d
coal
bonds,
these
and
s ite s
( 16) .
S o lv e n t Theory
Several
approaches
hav e
been
presented
to
bet ween s o l v e n t c h a r a c t e r i s t i c s
and t h e i r
Most
solvent
hav e o r i g i n a t e d
tio n
models:
Dr yden
assumed
to
solvents
u n its
theory
approaches
those o f
( 1 7)
be
act
asserts
pores.
structure
and
and
coal
co n sists
re la tiv e ly
sw e llin g
the
m ic e lle
w ith in
the
m ice lle
contained
enlarged
that
A
s u ita b le
s ta b iliz e
the
network
may
of
'm ic e lle s '
so
fragm ents
sm aller
through
therefore
that
that
Coal
that
d iffu s e
, must
t wo d i s s o l u ­
(17,18).
in d e s tru c tib le .
solvent
coal
p r o p e r t i e s on c o a l .
f r o m one o f
Dr yden and van K r e v e l e n
rig id
by
e x tra c tiv e
c o rre la tio n
are
sw ell
can
be
e x tra c tio n
m olecular
the
newly
the
transported
coal
to
the
s u rfa ce v ia osm otic d i f f u s i o n .
Van
Krevelen
( 18)
cro ss-lin ke d
polymer
He
that
believes
solvent
is
contends
and
the
amount
determ ined
S2 q = S2 d + 62 p + S2 h ,
hence
a
by
that
the
of
coal
p rin c ip le s
e xtra cta b le
that
can
of
viewed
polymer
m a te ria l
s o lve n t's
thermodynamic
be
theory
d issolved
s o lu b ility
property,
and
as
a
apply.
by
a
parameter,
the s o l u b i l i t y
5
O OH
OH OH
Figure
I.
S hinn's
Model
of
B i t u m i n o u s Coal
S tructure
6
p a ra m e te r -of th e c o a l .
a disp e rsio n
ponent;
component, a p o la r
Maximum s o l u b i l i t y
parameters o f
It
tio n
is
to
the
a
m ixture
(2)
the coal
( 1 9)
K revelin
solvents
not
be
the
has
presented
has
ideal
match th e
it
suggeste d
c rite ria
that
fo r
that
s o lu b ility
in d iv id u a l
is
comprised o f
obtained
when
bonding
the
com­
s o lu b ility
has made a s i g n i f i c a n t
by
then
be
to th a t o f
the
that
the
o ve ra ll
in d ivid u a l
param eter,
of
p o ssib le
s o lu b ility
an
ta ilo r
the
should
parameter
e xtra ctio n
s o lu b ility
be
parameters o f
to
By
the t a r g e t c o a l.
o v e ra ll
se le ctio n
s o lu b ility
suggesting
co n trib u ­
by u s i n g a m i x t u r e o f s o l v e n t s .
would
the s o lv e n t
evidence
o ve ra ll
is
c o m p o n e n t , and a h y d r o g e n
Hombach
van
parameter o f
Ward
the
of
of
parameter
and s o l v e n t a r e e q u a l .
that
work
of
s o lu b ility
p a r a m e t e r may be a d j u s t e d
s o lu b ility
of
the coal
p o ssib le
s o lu b ility
using
The o v e r a l l
may
so lve n t.
He
param eters, fu n c tio n s
ta ilo re d
the t a r g e t
so
that
they
coal .
TMU and HMPA
Hexamethylphosphoram ide,
solvents o f
a class
eac h
of
are
Iis te d
in te re s t
in
solvents
shown
in
In T a b l e
th is
ca lle d
Figure
pro p o rtio n s.
organic
prepared
solvents,
by
te t r a m e t h y lurea ,
in v e s tig a tio n .
d ip o la r
2
and
and
a p ro tic
some
of
TMU ,
are
the
HMPA and TMU a r e members o f
so lve n ts.
th e ir
The s t r u c t u r e s
physical
p ro p e rtie s
of
are
I.
HMPA i s a c o l o r l e s s
a ll
HMPA,
It
but
re a ctin g
m obile
is
not
also
w ith
liq u id ,
which
m iscib le
saturated
phosphorous o x i d e
w ith
is
m iscib le
many
p o la r
hydrocarbons
tric h lo rid e
w ith
and
(20).
w ith
water
in
nonpolar
HMPA
is
an e x c e s s o f
7
C6+
TMU
I
I
H3 C
CH3
O5 "
!I
HMPA
,N ^
V
\
F ig u r e 2.
Table
I.
Physical
Physical
P roperties
M o le c u la r Weight
Point
(°C)(1
M elting
Point
(°C)
Densi t y
( g / m l ) (25°C)
D ie le c tric
Constant
D i p o l e Moment
(debye)
-
^CH
^CH
5
S t r u c t u r e o f TMU and HMPA
o f TMU and HMPA
TMU
P ro p e rtie s
B o ilin g
c
atm)
HMPA
116.16
179-20
1 7 6. 5
235
- 1 .2
7 .2 0
0.9619
1 . 0 2 53
23.45
3 0 .0 0
3.37
5-37
8
d i m ethyl amine.
The
stoichiom etry
of
the
re a ctio n
is
shown
in
Equation
OPCi 3 + 6 HN(CH3 ) 2 — > OPfN(CH 3 ) 2 X3 + 3 H2 N(CH3 ) 2^ r
The
chemical
p ro p e rtie s
of
i o n i c c h a r a c t e r and p o l a r i t y
p a rtia l
negative
p a rtia l
p o s itiv e
atoms.
The
oxygen
charge
charge
at om make
hydrogen
n or ma l
Lewis
charge,
bond
b o ilin g
or
the
is
donor.
under
is
very
stable
but
The p r o d u c t s
bond
cloud
re a d ily
and
about
and
be
attack
+ H-A — > OP(H(CH ) 2 ) 2A + HN(CH3 ) 2
TMU
a
is
also
solvents
c o lo rle s s
as
w ell
as
pho sg e ne and d i m e t h y I ami n e as
a
the
poor
below
attacked
are
shown
TMU i s
sta b le at
co n d itio n s.
TMU u n d e r
le n t
its
by
in
liq u id
w ith
that
is
w ater.
m iscib le
TMU
illu s tra te d
in
( 2)
is
w ith
prepared
Equation
a ll
by
common
reacting
(3).
2 (CH3 ) 2 NH + COCl 3 — - > OC(NfCH 3 ) 2 X 2 + (CH3 ) 2 NH2V r
most
a
(2).
QP(N(CH ) 2 )
organic
d e n sity,
and p h o s p h o r o u s
acceptor
a c id ic
p a rtia l
atom,
tem peratures
can
of
the
oxygen
ele ctro n
at
to
e le ctro n
the n itr o g e n
hydrogen
co n d itio n s,
a cid s.
the
unhindered
e xce lle n t
HMPA
basic
and
over
due
A high
around
is d i s t r i b u t e d
HMPA an
p rim a rily
m olecule.
located
separation
Bronstead
Equation
of
HMPA a r e
(I)
severe
re a ctio n
tem peratures
Luttrin g h a u s
a c id ic
medium
b e i n g an e x c e l l e n t
( 21)
co n d itio n s,
fo r
solve n t.
many
below
its
has
but
nor mal
doc ument ed
contends
con d itio n s
and
is
(3)
b o ilin g
the
po in t
under
p rotonatio n
is
of
that
TMU
an e x c e l ­
very
u n r e a c t i ve w h i l e
9
The
author
exhaustive
refers
the
in fo rm a tio n
Luttringha us
(21)
fo r
The p h y s i c a l
many w a y s .
reader
concerning
the
works
the chemical
the p ro p e rtie s
and c h e m i c a l
Some o f
to
p ro p e rtie s
a
Both s o l u b i l i z e
a wide
( 20)
fo r
o f HMPA and t o
HMPA and TMU a r e s i m i l a r
t h e mos t n o t a b l e s i m i l a r i t i e s
Both a r e m i s c i b l e w i t h w a te r
N or mant
o f TMU.
p ro p e rtie s o f
a
of
in a l l
range o f
in
are:
p ro p o rtio n s.
o rganic
c ompounds ,
p a rtic u la rly
a r o m a t i c compounds.
Both
a
molecules
charge
and
a
hav e
an
p o s itiv e
over a ce n tra l
oxygen
charge
at om
that
at om and n i t r o g e n
A
B o t h hav e h i g h d i e l e c t r i c
a
Both a r e
liq u id
at
that
is
c a rrie s
d e lo ca lize d
a
by
negative
resonance
atoms.
constants
and l a r g e d i p o l e moments.
room t e m p e r a t u r e and have a w i d e
liq u id -s ta te
tem perature range.
A wor d
TMU and
ca ls
of
HMPA.
caution
The
is
probably
p a th o lo g ic
have n o t been v e r y w e l l
in
order
consequences
docum ente d.
p a r t i c u l a r may be a s k i n - c o n t a c t
s c ie n tis ts
It
2b) .
in
This
rea ctio n
the
hav e d oc um ent ed
hydrogenation
p r o c e s s has s i n c e
involves
the
of
been
rea ctio n
exposure
is
to
speculated
handling
these
that
of
chemi­
HMPA i n
Reaction
th e
n a s c e n t hydrogen formed from th e w a t e r - g a s
hydrogen
of
the
carcinogen.
Water-Gas S h i f t
Several
concerning
of
coal
s h ift
and c o a l
carbon
derived
of
name f r o m
products
s t eam
its
the
o ver elemental
(2 2 ,2 3 ,
The w a t e r - g a s
m o n o x i d e and
its
re a c tiv ity
reaction
1C o s t e a m . '
named
h y d r o g e n and c a r b o n d i o x i d e and d e r i v e d
enhanced
to
s h ift
produce
in d u s tria l
use
10
to
increase
of
s team
shown
t h e h y d r o g e n c o n t e n t o f w a t e r gas p r o d u c e d
w ith
hot
in E q u a tio n
c ok e
or
co a l.
The
sto ich io m e try
from
of
the
th e
reaction
reaction
(4).
CO + H2 O ----- » CO2 + H2
tu re
is
the
and
low t o m o d e ra te p r e s s u r e ,
lie s
there
rig h t
and
is
of
some
the
Van
and
The a l k a l i
(26)
is
shown
experim enta tion
of
th is
is
th is
Ness
water-gas
( 2 5)
over
s h ift
th is
believed
the pre se n t
in v e s tig a tio n .
Equation
for
Figure
that
th is
is
(3) •
was
(4).
tem pera­
very
m atter.
w ell
There
are
several
to
catalyze
mec hani sm
proposed
are
s h ift
Because
known
alm ost
conducte d
mec hani sm may
delinea ted
a ll
under
be o f
of
importance to
H0 CO
3.
P r o p os ed Mechani sm o f Aqueous A l k a l i
Water-Gas S h i f t C o n v e r s io n .
th e
a lk a lin e
2HC0
Figure
reader
inform ation
2H„0
H0 CO
th is
rea ctio n .
not
that
of
The
a d d itio n a l
s h ift
water-gas
in v e s tig a tio n
it
in
n on h o m o g e n e o u s ,
in
low
th e thermodynamic e q u i l i b r i u m
catalyzed
c o n d itio n s,
exp e rim e n ta tio n ,
the w a te r-g a s
controversy
homogeneous
in
as w r i t t e n
thermodynamics o f
re a ctio n .
E llio t
involved
the
Smith
mec hani sm
c a ta ly s ts ,
by
to
to
the
The
the
far
referred
regarding
and
con d itio n s
C+)
F or
rea ctio n
is
Catalyzed
R e l a t e d Work
To t h e
to e x tra c t
water-gas
a u th o r's
coal
knowledge,
w ith a stro n g ly
s h ift
re a c tio n .
the c o n ta c t o f coal
a sin g le
phase.
e xtra ctio n
of
coal
hydrogenation
c o m b i ne d e f f e c t s
coal
( 1 8)
hav e
solvent
fo r
a d e ta ile d
Work
van K r e v e l e n
solvent e x tra c tio n
parameter
Using
la rg e s t
close
to
e xiste d
of
to
fo r
coal
of
Good
those
o f water
of
work
th e s is ,
the
c u rre n tly
The
s c ie n tis ts
of
Dr yden
d is s o lu tio n
and
the
bitum inous
solvent
in
performed
he
fo r
coals.
s o l v e n t when c hos en w i t h
to
of
and van
th e o rie s
to
the
that
the
Krevelen
regarding
to
t h e i r works
of
Dryden
understanding
able
of
bet ween
parameter
coals
so lve n ts
to
of
and
of
the
the
have
good
a
s o lu b ility
the
g e n e ra lly
solvents
to
the
e xplain
so lve n t.
the
long­
exh ib ite d
the
coal
e x tra ctio n
s o lu b ility
parameters
Hombach was a l s o
respect
but
in v e s tig a te d .
referred
coal
was
mos t
poor
the
was a b l e t o d e m o n s t r a t e t h a t
of
bitum inous
( 17)
on
o f coal.
s o lu b ility
theory,
m ixture
is
subsequent
Hombach ( 1 9 )
e xtra ctio n
a
coal
re a ctio n ,
accepted
s ig n ific a n tly
d is s o lu tio n
that
been
s h ift
reader
the
that
coal
i n TMU and HMPA makes
has
water-gas
th is
co a l.
parameter
observation
dem onstrate
b e tte r
the
degree
so lve n ts.
in
of
by
in c o n j u n c t i o n wL t h th e
b o t h a t one t i m e have n o t been
o f co a l.
s o lu b ility
standing
the
have c o n t r i b u t e d
c o rre la tio n
solvent
study o f s o lv e n t e x t r a c t io n
performed
w o r k no o ne has a t t e m p t e d
b o t h w a t e r and a good
deal
many o f
e xtra ctio n
th is
o f w o r k has been p e r f o r m e d on t h e s o l v e n t
using
e a rlie r
form ulated
the
w ith
deal
o f using
As d i s c u s s e d
re a ctive
and a good
of
to
The s o l u b i l i t y
p o ssib le
A great
p rio r
fo r
the
coal
the s o l u b i l i t y
firs t
can
person
act
param eter.
as
a
12
The w o r k
in
that
using
of
th e y,
(2)
t o o , were
a m ixture
in d ivid u a l
Ward
of
and
able
Ichioka
su bstantia te
that
of
t o o b s e r v e enhanc ed d i s s o l u t i o n
a p p ro p ria te ly
s o lu b ility
(3)
c h o se n
parameters
so lve n ts.
instead
of
Ward
the
o f coal
suggests
o v e ra ll
s o lu b ility
tio n
that
in d iv id u a l
s o lu b ility
parameters o f
the
s o l v e n t m i x t u r e sh o u ld match th e
in d iv id u a l
s o lu b ility
parameters o f
the
ta rg e t
S ahin, a c o -w o rk e r, u n s u c c e s s fu lly
presence
of
overpressure.
sw e llin g ,
tio n
which
HMPA u s i n g
thw arted
Dr yden
(17)
permeate
c o a l-so lve n t
contact
Many s c i e n t i s t s
re a ctio n .
coal
met hod
extrac­
( 28)
of
Appel I
lite ra tu re
The
e x t e n s i ve
of
on c o a l
work
to
observations
of
be
bed
reactor
handling
as t h e f i r s t
to
plug
up and
incorporate d
if
coal
in
hydrogen
problems.
Sahin d e te rm in e d
be
and
step o f
Coal
the e x t r a c ­
v irtu a lly
that
no
some o t h e r
these
hydrogenation o f coal
F ischer
is c r e d ite d w ith
low
is
hydrogenate
hav e s t u d i e d
in itia te d
s o lu b iliz a tio n
to
m a te r ia ls-
be e l i m i n a t e d .
( 27)
use o f c a r b o n m o n o x i d e and w a t e r
A ppel I
m a te ria ls
plug.
mus t
trie d
p ac k ed
id e n tifie d
the
problem s were t o
gas s h i f t
by
a
c aus ed t h e pac k ed bed r e a c t o r
could
handling
TMU and
He was
process,
solvent
work
coal
coal .
I.
the
ideal
that
fo r
He c o n t e n d s
the
by
p a r a m e t e r s h o u l d be t h e c r i t e r i a
so lve n t.
engine ering
Hombach
a
rank
often
fo r
the
su b sta n tia l
coal
w ith
quoted
in
firs t
hydrogenation
research
carbon
current
using
documenting
of
c o a l.
e ffo rt
monoxide
the w a te r-
to
and
watef-gas
Later,
study
w ater.
s h ift
the
the
The
reaction
hydrogenation.
A ppel I
et
aI .
on
covered
in
any
d e ta il
he has made s h o u l d
coal
hydrogenation
in
be p r e s e n t e d .
th is
For
is
th e sis,
coal
fa r
but
too
some
hydrogenation
13
using
t h e w a t e i — gas s h i f t
4500 p s i
and r e a c t i o n
tem peratures
d o c u m en t e d t h e f o l l o w i n g
A
Conversion
reaction w ith
of
in
carbon monoxide o v e r p r e s s u r e s o f
th e
r a n g e o f 3 7 5 _4 0 0 ° C ,
Appell
has
greatest
fo r
fa cts:
coal
to
so lv e n t-s o lu b le
products
is
low rank c o a l s .
Conversion
a
1000
increases
psi
and
then
w ith
carbon
increases
monoxide
o nly
overpressure
s lig h tly
w ith
up
to
a d d itio n a l
pressure.
a
Conversion
increases w it h
a
Conversion
is
as w i t h
A
A ppel I 1s
rea ctio n
products.
to
may i n h i b i t
et
h av e
al .
of
(23)
revealed
There
coal
carbon
monoxide
causes c o n v e r s i o n
overpressure
he
has
that
concluded
re a ctio n s
the
low rank c o a l s
is
the
some
water-gas
im portant
these fa c t s
a dram atic
when
is g r e a te r
the
to drop.
mos t
is
that
that
pH o f
than
s h ift
fa cts
re la tiv e
increase
the
water
c o n trib u tio n
the a c tiv a te d
on t h e h y d r o ­
Ross's
in v e s tig a ­
n o t document ed by Appel I .
in ve stig a tio n
the s o lv e n t- s o lu b le
fo r
the
water-gas
The
are:
fra c tio n
s h ift
12. 6 .
Basic w a te r s o l u t i o n s
in s o lu b le
re a ctio n .
re a ctio n .
to th is
in
w ater-gas
to
s ig n ific a n t
p r o b a b l y due t o
s h ift
the
lead
have a l s o p e r f o r m e d e x p e r i m e n t a t i o n
using
most p e r t i n e n t o f
A
w ith
s p e c i e s f o r m e d by t h e w a t e r - g a s
genation o f coal
a
great
condensation
He has a l s o c o n c l u d e d
Ross
tio n s
to a i r
observation s
the s o l u b i l i z a t i o n
hydrogen
as
tem perature.
hydrogen o v e r p r e s s u r e .
Exposure o f coal
From
s h ift
tw ice
increasing
a l o n e do n o t e nhan ce s o l u b i l i t y .
of
re a ctio n
14
The
a
us e
of
con d itio n s
Ross
has
hydrogen
does n o t p r o m o t e
suggested
that
hydrogenation o f coal
Takemura
tio n
of
and
coal
the
(24)
carbon
of
A ppel I
g e n o lysis
nascent
coal
of
the
fragm ents
using
th is
met hod
p re vio u sly
and
as a c a t a l y s t
the
water
of
three
in -s itu
zin c-w a te r-co a l
best
T hese
lend
hydrogen
species
w ith
th e ir
w ith
c a ta ly tic
in
the
fo r
the
study
liq u e fa c­
presence
of
a
roughly p a r a lle l
have p r o p o s e d
routes:
that
hydrogenolysis
w a t e r , and
is
the
nascent
rea ctio n
on
coal
referred
to
these s tu d ie s
rea ctio n
hav e s t u d i e d
hydroby
s ta b iliz a tio n
the
of
coals
using
products
been
w orking
hydrogen
model
fo r
made
better
that
observation s
w ith
the
made by
water-gas
that
higher
s h ift
the nascent
d is s o lu tio n .
attem pt
formed
in fo rm a tio n
at
w ith
the s p e c u la tio n
compounds
id e n tifie d .
the w a te r-g a s
the hydrogenation o f
and w o r k s
co n siste n t
to
than
Mondragon has d oc um ent ed t h a t
t h e k e y t o e nhan ced c o a l
have
by
are
rank
evidence
studies
of
( 27)
in v e s tig a to rs
c re d ib le
by me th od s o t h e r
re a ctio n .
low
re s u lts
mentioned
and
and t h e
investigate d
reaction
Mondr agon e t a l .
rea ctio n
re a c tiv ity
be f o r m e d
works
Several
by
basic
con d itio n s.
Takemur a and Ouchi
s o lv o ly tic
can
the
tem peratures.
s h ift
under
s o lu b ility .
may a c t
The r e s u l t s
occurs
monoxide
in a v e h i c l e o i l .
re a ctio n .
coal
ion
monoxide
R oss.
coal
hydrogen,
H y dr ogen
s h ift
and
have
carbon
increased
under w a te r-g a s
Ouchi
using
of
form ate
cobalt-molybdenum c a t a l y s t .
those
instead
in
to
the
ch a ra cte rize
water-gas
(27,28,29,30) .
regarding
the
s h ift
The r e a d e r
model
the
is
compounds
15
Research O b j e c t i v e
The
o b je c tiv e
d ip o la r
a p ro tic
on
e x tra c tio n
the
of
th is
solvents
of
TMU and
co a l.
was t o be c o r r e l a t e d w i t h
ature,
carbon
in itia l
so lve n t.
residue
a fte r
inary
study,
e x tra c tio n
p r o c e s s and
monoxide
was
re a ctio n
to ta l
to
was
evaluate
of
be e v a l u a t e d .
intended
v a ria b le ,
o f prom ising
but
to
v a ria b le .
a ctio n
s h ift
of
re a ctio n
so lve n t
not
the
w ater-gas
e x tra c tio n
the q u a n t i t y
a s s o c i a t e d w i t h eac h
id e n tific a tio n
to
HMPA u n d e r
overpressure,
research
eac h
was
the experim ental
e xtra c tio n
trends
be e v a l u a t e d .
The
A d d itio n a lly ,
th is
c h a ra cte rizin g
research
:
the
coal
and
the
c o n d itio n s
observed
v a ria b le s o f
blend,
of
pH
temper­
of
solvent
re tained
Designed
t o be a p r e l i m ­
to
be
in
the
exhaustive
determ ine
the
The. v i a b i l i t y
research-work d ir e c tio n s
the
in
general
of
th is
w er e t o
16
EXPERIMENTAL
Raw M a t e r i a l s
C o ls trip
sub-bitum inous
work performed
the
crushing
m ill
Montana.
As
diam eter
from
trans i t ,
the
received
in t h i s
of
Western
was
used
coal
e x c lu s iv e ly
of
located
in
p a rtic le s
approxim ate ly
a t Mont ana S t a t e U n i v e r s i t y ,
60
atm ospheric
t o be a b o u t one w eek .
th is
in v e s tig a tio n .
fe llo w
student
atm ospheric
since
from
and
the
the
is estim ated
Bakerstown
The
at
Savage
Mont ana
c o n d itio n s,
and
it
sampl e' was m i n e d .
mine
in
Preston
the
same
method.
m ill
w h ile
ated
fo r
Each
under
about
atmosphere,
coal
County,
sample
the
using
were
was
a n itro g e n
and s i z e d
in
W hile
in
When
s a m p l e was
w e r e used on a l i m i t e d
lig n ite
s am pl e
U n iv e rs ity .
not
the coal
known
Bakerstown
West
was
It
V irg in ia ,
in
from
a
obtained
was
how much
coal
basis
stored
tim e
had
was o b t a i n e d
and
was
under
elapsed
d ire c tly
stored
under
in t r a n s i t .
samples
2k h o u r s
is
The
atm ospheric c o n d itio n s w h ile
Al I o f
coal
State
ranging
t h e s a m p l e was p l a c e d u n d e r n i t r o ­
exposed t o
lig n ite
from
co n d itio n s.
The t i m e t h a t
Savage
the
Col s t r i p ,
mesh.
gen t o p r e v e n t any f u r t h e r o x i d a t i o n .
th e atm osphere
in
s am pl e was o b t a i n e d
Corporation
under
stored
was
alm ost
consisted
to
i nch
R eagen ts
The c o a l
Energy
the
one
coal
coal
in v e s tig a tio n .
r e c e i ved ,
about
and C h e m i c a l
sized
loaded
fo r
in to
atm osphere .
s a m p l e was
experim ental
a
A fter
tw o -lite r
the
b a ll
removed, w h i l e
standard T y le r
screens.
use u s i n g
porcelain
m ill
the
ba ll
had o p e r ­
under a n itro g e n
Only sample m a t e r i a l
17
ranging
in
m ate ria l
size
was
from
stored
60
to
under
100
mesh
was
re ta in e d .
a n itro g e n
atm osphere
p u rity
the
The
u n til
sized
used
s am pl e
fo r
e xp e ri-
m e n ta tio n .
The
used
in
m anufacturer
th is
was p e r f o r m e d
T a b le 2.
and
in ve stig a tio n
to confirm
C hem ic al
of
a r e shown
the p u r i t y
in
of
so lve n ts,
Table
2.
reagents,
No a d d i t i o n a l
P u rity
Source
A ld ric h
C hem ic al
99%
HMPA
A ld ric h
C hem ic al
99%
T e t r a l ine
A ld rich
C h e m i c al
99%
Sodium H y d r o x i d e
C h e m i c al
Stockroom
Unknown
H ydrochloric
C hem ic al
Stockroom
Unknown
Acid
Acetone
VanWat er s S Roger s
99.5%
Carbon M o n o x i d e
A irco
99-9%
N itrogen
L iquid A ir
Experimental
The a p p a r a t u s used
d e ta ile d
p e rtin e n t
tio n a l
of
c a ta ly tic
drawing
m ixing
apparatus
of
the
mechanical
a g ita tio n
in
th is
reactor
reactor
Apparatus
experim entation
manufactured
vessel
c h a ra c te ris tic s
shown
the
reactor.
in
F i g u r e 5•
9 8 . 6%
Corp.
is
are
v a n e was added t o t h e
w ith in
is
te s tin g
these chem icals.
TMU
s tirre d
g as es
R e a ge n t s Used
Chemi c a l
c a lly
and
A flo w
was a m o d i f i e d
by A u t o c l a v e
shown
lis te d
reactor
scheme
in
in
Engineers.
F igure
Table
m agneti­
4,
3-
and
A
the
An a d d i ­
to enhance th e t u r b u l e n c e
fo r
the
reactants
in
the
18
VENT L IN E
THERMOCOUPLE PORT-----
NITROGEN INLET
CARBON MONOXIDE INLET
MAGNETICALLY DRIVEN SHAFT
SOLVENT INLET
F i g u r e 4.
M a g n e tica lly
S tirre d
R eactor.
PRESSURE GAUGE
THERMOCOUPLE
REACTOR
NITROGEN TANK
P O S IT IV E DISPLACEMENT PUMP
F i g u r e 5-
Flow Diagram f o r
Experim ental
Reactor.
20
T a b l e 3.
S p e cifica tio n s
o f M a g n e tica lly
S tirre d
R eactor.
Spec I f i c a t i o n
I tern
S A - I 8 2 - F 3 16
Reactor M a te ria l
S tainless
R e a c t o r Vol ume
19.4 c u b i c
Working
O - 36 OO pounds p e r s q u a r e
Pressure
Steel
inches
inch
Working Temperature
72-1000 degrees
A g ita to r
0 -2 50 0 r e v o l u t i o n s
per m inute
pump
by
Speed
An a d j u s t a b l e
capable
of
rea ctio n
p o s itiv e
70.0
d e liv e rin g
displacem en t
cc/hr
was
used
manufactured
to
intro d u ce
Mi I r o y a l
solvent
to
the
v e s s e l.
Coal
residues
vacuum
filtra tio n
filte r
paper.
were
separated
fla s k
fitte d
from
w ith
a
the
e x tra c tio n
conical
w e r e made u s i n g
funnel
The
an
Orion
b u ffe r
Model
901 m i c r o p r o c e s s o r
io n a lyze r
s y s t e m was used t o c a l i b r a t e
p re paratio n,
out
and
using
a
Whatman
t h e s o l v e n t m i x t u r e s and e x t r a c t i o n
a r e s e a r c h g r a d e pH e l e c t r o d e and a d o u b l e j u n c t i o n
A t wo s o l u t i o n
solvents
#1
The i n - h o u s e vacuum was used as t h e vacuum s o u r c e .
The pH m e a su r e m e n t s o f
ca rrie d
Fahrenheit
storage,
under n i t r o g e n
Vacuum/Atmospheres
and
handling
of
products
fitte d
w ith
reference e le c tro d e .
the appara tu s.
the
coal
s am pl e s
were
i n a D r i L a b H E - 4 3 - 2 g l o v e box m a n u f a c t u r e d by
C orporation .
The
s a m pl e s
were
a lso
weighed
in
the
g l o v e b o x.
Ash a n a l y s e s
of
at
M e ttle r
le a s t
were
7 5 0° C .
H80 a n a l y t i c a l
performed
The
weights
balance.
using
of
a high
the
tem perature
oven
s am p l e s w e r e meas ur ed
capable
using
a
21
'
Elem ental
performed
analyses
using
i n t e g r a t o r and
a
(C,H,N)
C arlo
Erba
interfaced
were weighed f o r
of
the
Elemental
the elemental
pre-weighed
introduced
to
im m ediately
a
coal
reactor
sealed
approxim ately
and
fiv e
reactor
in ternal
During
the
tim e
Sodi um
hydroxide
m ixtu re
to
tem perature,
A fte r
to the
speed
system
p sig .
the
the
pH.
ju s t
p rio r
to
reactor
adjusted
the
to
tem perature.
nitrogen^
power
the
to
its
la rg e
was
acid
th erm al
in
the
rate
Carbon
the
The r e a c t o r was a l l o w e d
then
was
reactor
was
mass o f
up,
purge o f
of
the
th e system,
power
to
the
solvent
to the
of
solvent
was
reactor
s tirre r
was
to
o f w ater.
the
was meas ur ed
solvent
at
room
reactor.
s o l v e n t was
about
monoxide
the
t o 7 ml
added
150 ml o f
The m a g n e t i c
rpm,.
grams
m antle
applying
heating
was
p e rio d ,
flo w
fiv e
The
heating
a fte r
in tro d u ctio n
a volu m e tric
pressure
The s a mp l e s
to approach steady s t a t e .
reactor
w ar m- u p
1000
were
a DP 110
A fte r a n itro g e n
the
required
The pH o f
pump.
w ith
m icrocom puter.
approxim ately
room
tem perature
adjust
the
the
h yd ro ch lo ric
displacem en t
and
at
that
fitte d
143 ml o f TMU, o r TMU-HMPA m i x t u r e ,
or
reactor at
p o s itiv e
vessel
15 h o u r s w e r e
the
p repared by adding
w eighing
Bec aus e o f
fo r
residues
Procedure
sample
m in u te s,
12 t o
approxim ately
I
coal
a n a l y s e s u s i n g a. Cahn 29 e l e c t r o b a l a n c e .
purged w i t h
r e a c t o r was t u r n e d o n .
and
Analyzer
w i t h an O s b o r n e
Experim ental
A
coal
15 m l / m i n ,
introduced
using
was a c t i v a t e d
was
introduced
generally
t o o p e r a t e f o r one h o u r .
adjusted
the
and t h e
to
the
to
500
22
was
A fter
the
reactor
had o p e r a t e d
turned
o ff
and
power t o
the
The r e a c t o r was a l l o w e d
The
w ith
g a se s
n itrogen
contents
w ith
in
fo r
removed
acetone to
The
solvent
was
m inutes.
The
a vacuum -suction
w ith
used
to
clean
residue
it
acetone
the m agnetic
and
m ixture
was
u n til
the
opened
rem aining
then
purged
and
the
filte re d
The c o a l
e fflu e n t
residue.
filte re d
Watman #1
was
contained.
was
The r e a c t o r was washed
amount s o f
reactor
reactor
was
device.
turned o f f .
hours.
the
reactor
preweighed
the
ten
s tirre r
filte r
in
a
paper.
to. r e c o v e r t h e
residue
appeared
filte r-c a k e
cle a r
and t h e
appeared d r y .
a vacuum
weighed
vented
fla s k
The f i l t e r - c a k e
to
were
residue
washed w i t h
filte r-c a k e
reactor
fitte d
hour,
approxim ately
c o a l-e x tra c t
amount o f c o a l
then
fo r
remove and r e c o v e r s m a l l
The a c e t o n e wash
was
one
t h e h e a t i n g m a n t l e was a l s o
to cool
1 0 - 15
using
vacuum f i l t r a t i o n
small
the
fo r
pump
was p l a c e d
capable
p e rio d ic a lly
detected
bet ween
residue f i l t e r - c a k e s
and
of
i n a vacuum d e s i c c a t o r
approxim ately
deemed,
weighings
dry
at
0. 1
when
no
d a ily
to rr .
The
s ig n ific a n t
in te rv a ls .
were c o n s id e r e d d r y a f t e r
t h a t was a t t a c h e d
Mos t
residue
weight
of
was
c h ange
the
coal
a p p r o x i m a t e l y one week i n
the d e s ic c a to r .
A n a lytica l
Water
analyses
a va ila b le
oven
p o rce la in
cru cib le s
The
s am p l e s
were th en
on
the
o p erating
were
removed
and
placed
at
coal
samples
103°C.
weighed
in
Procedure
the
on
The
a
d ryin g
from the o v e n ,
were
coal
M e ttle r
oven
allow ed
fo r
carried
out
s a m pl e s
H80
24
to cool
in
were
a n a ly tic a l
hours.
to
an
a ir-
placed
in
balance.
The s a mp l e s
room t e m p e r a t u r e .
23
and w e i g h e d .
loss.
The
The l o s s ^ i n w e i g h t o f
assumption
of
water
the
loss
samples
w ill
be
was a t t r i b u t e d
addressed
la te r
to
in
water
th is
th e sis.
Ash
s a m pl e s
ashing
analyses
in
on c o a l
p o rce la in
ov en
samples
c ru c ib le s
o p e ra tin g
at
were
and
performed
in s e rtin g
7 5 0° C .
The
s am p l e s
(C,H,N)
of
the
by
them
placing
in
an
w er e a l l o w e d
preweighed
a ir-a v a ila b le
to
remain
in
t h e oven f o r 2h h o u r s .
Elemental
analyses
performed
by
the
author
ated w ith
the o p e ra tio n
using
standard
coal
and
q u a n tita tiv e
o f a C a r l o Er ba e l e m e n t a l
coal
residues
procedures
were
a sso ci­
a n a l y s i s machine.
2k
RESULTS AND DISCUSSION
Total
C o ls trip
r a n g ed
e x tra c tio n
from
10 t o
are
Temperature - -
a
CO o v e r p r e s s u r e
A
Reaction
A
Solvent
blends - -
a
Solvent
pH - -
Because• o f
high
residue
and
re s u lts .
residue
It
w ater
re s u lts
that
m in e ra l-m a tte r
and o t h e r
35 p e r c e n t .
a
apparent
a
sub-bitum ino us coal
achieve these
tio n s
on
--
a lso
be
n itro g e n
co n ce n tra tio n s
amount s o f
com plicated
discovered
v o la tiliz e d
Equation
of
(5).
solvent
the
regarding
e xtra ctio n
using
con d itio n s
used t o
TMU-H2 O, TMU-HMPA-H2 O, T M U - H M P A - T e t r a l i n - H 2O
the
that
at
the
the
were
the
coal.
be p r e s e n t e d
of
of
it
was
the
coal
e xtra ctio n
n itro g e n
in
in
the c o a l .
compounds o t h e r
The
la te r
the
10 0 - 103 ° C , c o n d i ­
of
co a l,
in
the
the e x t r a c t i o n
tem peratures
of
residue,
retained
concentratio n
the d ry in g
from
in
in te rp re ta tio n
to c a lc u la te
C a lcu la tio n s
calcu la te d
re a ctio n
in v e s tig a tio n
below:
d i s c o v e r y and d o c u m e n t a t i o n w i l l
A bsolute
th is
I hour
norm ally associated w ith
mus t
in
fo r
250-1000 p s ig
had t o be made i n o r d e r
was
used
basis
7- l k
s ig n ific a n t
Assumptions
w a te r-fre e
25-205°C
tim e - -
somewhat
coals
The r a n g e o f
lis te d
and
s p e c ific s
in
th is
of
than
th is
section.
and A s s u m p t i o n s
o rg a n ic
m atter
of
coal
s a mp l e s
was
25
AE = WC* CWA - WR-'-RWA-RS
(5)
WC* CWA
where:
AE
= absolute e x tra c tio n
WC
= w eight o f coal
has i s
on an a s h - and w a t e r - c o n t a i n e d
CWA = c o r r e c t i o n f a c t o r
in th e coal
WR
The v a l u e
the
co a l,
m atter
coal
was
= w eight o f s o lid
residue
factor
f o r w a t e r and as h
RS
= co rre c tio n
fa cto r
fo r
of
CWA,
the
calculated
le ft
in
a l s o assumed t h a t
an a i r - a v a i l a b l e
CWA = I
f o r w a t e r and ash
RWA = c o r r e c t i o n
r e s ! d ue
conventional Iy
when
to c o rre c t
co rre ctio n
using
as
an a i r - a v a i l a b l e
combustion o f
fo r
( 6) .
It
"m oisture"
ov en
at
the coal
a s h i n g ov en o p e r a t i n g
-MW-
fa cto r
Equation
described
solvent
the
residue
the w ater
was
the
and
assumed
fo r
com plete
ash
from
the
It
was
24 h o u r s .
a fte r
in
th a t only
was v o l a t i l i z e d
I 03°C
was
in
in
24
hours
in
a t 750° C.
(6)
MA
where:
MW = mass f r a c t i o n o f w a t e r
w e t-c o a l basis
MA = mass f r a c t i o n
The
the
that
value
of
residue,
was
o nly
water
RWA,
the
calculated
was
in th e coal
o f as h on a w e t - c o a l
co rre c tio n
using
v o la tiliz e d
fa cto r
Equation
from
fo r
( 7) •
the
on a
basis
the w ater
Again
it
r e s i d u e when
and
was
ash
in
assumed
le ft
i n an
26
a ir-a v a ila b le
a fte r
oven
combustion
RWA = I
at
103OC f o r
24 h o u r s .
i n an a i r - a v a i l a b l e
- MWR-
Ashing
ov en f o r
was
assumed
complete
24 h o u r s a t 7 5 0° C .
MAR
(7)
where:
MWR = mass f r a c t i o n
o f water
MAR = mass f r a c t i o n
o f ash
Because o f
became
the
e vid e n t
residue.
its e lf
as
a
that
solvent
retained
o f m ate ria l
of
c o rre ctio n
the
residue
n itrogen
as
b e c a us e mos t
Model
s h ift
the
a
the
of
rings
that
the
the
coal
were
be
n itro g e n
coal
in
so
by
.reader
is
v e rify
the expected p o s it io n
retained
in
so t h a t
the
firs t
have
is
Lynch
of
m anifests
the
the t o t a l
amount
is
that
fra c tio n
v a lid
up i n a r o m a t i c
rin g s.
demonstrated
the
ring
does
concentrated
the coal
under
not
in
the
structure
in
was
probably
have
w ith in
re te n tio n
same mass
hydrogenated
o f n itro g e n
t h e amount
so lve n t
are
coal
The u se o f
assumption
tie d
( 30)
d is trib u tio n
proposed
were
residue
assumption
coal
be n e i t h e r
its
it
to q u a n tify
that
The
This
the
residue,
be e s t i m a t e d .
would
n itro g e n
w ill
the
could
basis
h yd ro lysis
r e s i d u e because o f
to
the
the
d e g r e e of. e x t r a c t i o n .
required
performed
con ta in in g
but
content o f
residue m a trix
co a l.
n itro g e n
studies
residue
fragments
in
ca lcu la te d .
o rig in a l
referred
so lve n t
observed
s o lv e n t-fre e
the
solvent
from th e coal
could
c o n d itio n s,
thought
in
on
compound
arom atic
the
assumptions
fa cto r
of
the re s id u e
f a c t o r , RS, was an a t t e m p t
in
extracted
Several
and/or
Incorporatio n
low ering
solvent
in
the e x c e s s iv e ly high n itr o g e n
the s o lv e n t c o r r e c tio n
of
in
coal
shown
water-gas
occur.
the
in
m a trix.
that
It
is
products
nor
m a trix.
The
Figure
I to
27
tio n
The second a s s u m p t i o n made i n
the c a lc u la t io n
fa cto r
does
was
con d itio n s
that
the
encountered
solvent
in
th is
the
should not
reaction
be s e v e r e enough t o
unable to v e r i f y
It
the
was
solvents
were
were a v a i l a b l e
A more
used
re lia b ility
The
free
are
of
w ishing
tio n s
the
to
th is
same
the
the
and Normant
experim entation
b u t t h e a u t h o r was
of
solvents
ra tio
in
T h is assumption
possib le
fa cto r
is
has
balance
the
in form ation
to
molar
errors
were u se d ,
the
residue
is dubious a t
associated
presented
the
so lve n t-co n ta in in g
generate
referred
in
in
the
as
best.
w ith
each
errors
and
th e sis.
elem ental
a d d itio n a l
is
the
when m i x t u r e s
c a lcu la tio n s
gram o f
fo u r
required
that
of
co rre c tio n
per
reaction
reta in e d
in. t h i s
f r a g m e n t TMU and HMPA,
in
discussion
section o f
residue
was
the
by L u t t r i n g h a u s
encountered
the b u lk s o lv e n t.
solvent
so lu tio n
assumed
in
and
under
reten­
in h is e x p e r im e n t a t io n .
retained
in
thorough
assumption
th is
further
As r e p o r t e d
con d itio n s
the s o lv e n t
fragment
in ve stig a tio n
r e s i d u e as a c o m p l e t e m o l e c u l e .
( 2 0 , 21) ,
not
of
Appendix
of
grams
residue.
equations
solvent
on
u n its
The
of
sim ultaneous
and a c o n s t r a i n t
c o rre ctio n
the
solvent
B,
where
fa c to r.
re te n tio n
a
sample
solvent-
equation
The
reader
fa c to r ca lc u la ­
c a lc u la tio n
is
iI lu s tr a te d .
Al I o f
the
tio n
are
that
d e ta ils
shown
in
calcu la te d
raw data, g e n e r a t e d d u r i n g
presented
to
the e n t i r e
Appendix
a r e shown
B.
the
reader
in
c a lc u la tio n
The
re s u lts
i n A p p e n d i x C.
the
course o f
A p p e n d i x A.
th is
A sample
in v e s tig a ­
c a lc u la tio n
s e q u e n c e f o r one e x p e r i m e n t a l
of
a ll
of
the
e x tra c tio n
r un
is
runs
as
28
E r r o r and R e l i a b i l i t y
This
such,
in ve stig a tio n
more e m p h a s i s
c h a ra c te ris tic s
was
has
fo r
designed
been
placed
sp e cifie d
o f Meas ur ement s
to
on
rea ctio n
be
cursory
d e te ctin g
in
nature,
trends
parameters
than
in
in
and
as
e xtra ctio n
documenting
the ex ac t magnitude o f e x t r a c t i o n .
G r e a t c a r e was t a k e n d u r i n g
cal
me th od s
s p ite
of
used
the
in
fact
su b je ctive
in
e xtra ctio n
value.
Equation
Table
the
experim entation
were
an
used
term
is
in
used
inherent
reader
the
in
to
has
been
considered
several
the
assum ptions
of
c a lc u la tin g
absolute
error
Appendix
accurate
e x tra c tio n
and
those
D fo r
are
data.
In
t h a t were
the
coal
equatio n,
shown
in fo rm a tio n
on
in
how
e r r o r v a lu e s were e s t a b l i s h e d .
R e la tive
E r r o r o f Measurements.
R e la tive E rror
V aria b le
it
p r o c e d u r e and a n a l y t i
o b ta in
course
re la tiv e
referred
T a b le 4.
Using
to
c a u t i o n was t a k e n ,
Each
has
The
re la tiv e
that
nature
( 5).,
4.
th is
the experim enta l
the e r r o r
WC
±0.1%
WR
±2.0%
CWA
±0.5%
RWA
±0.2%
RS
±1.9%
p r o p a g a t i o n met hod o u t l i n e d
calculated
average,
may
that
be
the
e x tra c tio n
high o r
value
by M i c k l e y e t a I .
fo r
l o w by as much as
run
17 ,
4.0
(31)>
which
is
percentage
29
p o in ts.
extend
The
4.0
length o f
author
error
bar
percentage
the e r r o r
has
e x tra c tio n
to
in
a ll
p o in ts
bars
c hos en
values
fo r
is
illu s tra tio n s
a weak
amount
has
of
long
m oisture.
tra d itio n a lly
coal
in
an
loss
to
that
before
been
oven
and
that
The
amount
10 0 - 1 03°C
a fte r
the
T a b l e 5•
Elemental
low
value.
e x tra c tio n ,
constant
loss.
rank
of
by
m oisture
d ryin g
over
contain
in
a
fre s h ly
the
a
coal
The
but
the
r a n ge
of
analysis
of
procedure
s ig n ific a n t
s am pl e
ground
and a t t r i b u t i n g
be v o l a t i l i z e d .
s a m p l e s a r e shown
Ana l y s i s
a
hours
Elemental
standard
coals
d ryin g
2k
fo r
t h a n w a t e r mus t
t h e w e t and d r y c o a l
error
the
should
D r y i n g Anomal y
known
water
of
17
in v e s tig a tio n .
chara cte rize d
at
of
compounds o t h e r
fo r
been
fu n ctio n
the
The Coal
It
r un
a bo ve and b e l o w t h e c a l c u l a t e d
consider
th is
showing
a
has
has
sampl e
of
the weight
C o ls trip
coal
revealed
that
The e l e m e n t a l
analyses
i n T a b l e 5.
f o r Wet and Dr y C o a l .
Weight Percent
Elemental
A nalysis
Ash
Content
N
C
H
Wet
0.92
56.6?
4.48
Dr y
1 . 13
67-55
4.58
C o ls trip
Coal
8.04
(9.78)*
“ C alculated'
Using
of
17. 8
a
10 0 - g r a m ,
percent,
the
wet-coal
gram-mole
basis
loss
I t was assumed t h a t no ash was l o s t
of
and a measur ed " m o i s t u r e " c o n t e n t
eac h
during
element
can
be c a l c u l a t e d .
d r y i n g and t h e o x y ge n c o n t e n t
30
of
the
coal
c a lc u la tio n
could
be
calculated
Gr am- Mol e
Loss
to
assumed
account
to
be
fo r
0.000
0.095
0.720
0.997
a ll
of
In
the
methane, w a te r,
are
See A p p e n d i x
E fo r
w ill
the elemental
s a tis fy
Research
tiliz e d
in
d ire cte d
the
conceivable th a t
o ff
of
d e riv a tio n
at
drying
is
a
if
the
complex
process.
carbon
the coal
of
a
and
during
products
of
small
the d ry in g
com bination
are
gas es
are
of
it
amount s o f
procedure.
compounds
which
in T a b le 6 .
shown
id e n tify in g
e xa ctly
is
m ixture
lib e r­
Although not v e r i f i e d ,
loss values
procedure
hydrogen
o ff-g a s
d io xid e ,
what
recommended
p r o d u c t s o f v a l u e may be
recovered a t minimal
in s u ffic ie n t
oxygen
the drying
driven
the
there
re a lity ,
is
compounds
( g m o l e / l O O g w et c o a l ) .
0
during
other
that
H
w ater.
that
of
C
pro b a b ly given o f f
suspected
re s u lts
N
As can be seen f r o m T a b l e 6 ,
ated
The
d iffe re n ce .
in T a b le 6 .
a r e shown
Gr am- Mol e E l e m e n t a l
Table 6 .
by
m a te ria ls
by
id e n tifie d
the
in
are
author.
the
v o la ­
It
off-gas
is
and
expense.
Temperature E f f e c t s
A series
on
the
o f e x p e r i m e n t s was r u n t o a s s e s s t h e e f f e c t o f
e x tra c tio n
o f ,Col s t r i p
The s o l v e n t c o n s i s t e d o f
s o l v e n t was a d j u s t e d w i t h
th an
12.
In a l l
runs
coal
under
water-gas
s h ift
143 ml o f TMU and 7 ml o f w a t e r .
s o di u m h y d r o x i d e and
in
a ll
tem perature
co n d itio n s.
The pH o f
cases
the
was g r e a t e r
t h e c a r b o n m o n o x i d e o v e r p r e s s u r e was m a i n t a i n e d
at
31
500 p s i g .
there
A p lo t o f
is
little
contrary
tio n s ,
or
the
re s u lts
he o b s e r v e d an
by Appel I
increase
in
cases
no
tem perature
under pure s o lv e n t e x t r a c t i o n
co n d itio n s.
Several
that
a b ov e
factors
the
so fte n in g
suspected
that
There
extract
been
is
in
a d iffe re n t
also
has
a very
range
of
removed.
large
so lve n t,
of
below
f o r approxim ately
The
the
It
is
p re c ip ita te d
b e c a us e
of
e x tra c tio n
the v a rio u s
coal
and n o t a m e as ur e o f
would
then
total
that
( 16)
some
solvents
fo r
the f a c t
where
a tempera­
encountered
of
coal,
in
th is
p o ssib le
the
some
in
th is
and
it
is
a ll
of
The
the
e ffe ct
coal
would
is o la te
reactor
rea ctio n
the
vessel
products
were
c a s e s was f i l t e r e d
the
extracted
s o lu b ility
the s o lv e n t a t
during
coal
at
m aterial
ca p a city
a meas ur e o f
o ccu rrin g
of
in ve stig a tio n
to
be s a t u r a t e d w i t h
be o n l y
in
lim its
in
reaction.
lim ite d
e x tra c tio n
increasing
t e m p e r a t u r e was a t o r
p o in t
not
m ixtu re
e x t r a c t molecules
co n d i­
Bodegom
and a t e m p e r a t u r e
before
in w hich case th e s o l v e n t c o u ld
The o b s e r v e d
s h ift
w ith
fo r
s o lu b ility
is
the
a
r e s u l t appears
Van
cases
be s ee n ,
mec hani sm may be i n v o l v e d .
it
12 h o u r s
p ossible
the
a p p a r a t u s used
a fte r
so lve n t-c o a l-re s id u e
In
that
and
can
t h a t may a c c o u n t
so fte n in g
have been r e a c h e d
im m ediately
400°C.
Temperatures
e x tra c tio n
mas s,
o f coal
the re a c tio n
co a l.
p o s s ib ility
thermal
room t e m p e r a t u r e .
have
( 22) ,
This
d ep en d en ce
id e n tifie d
The e x p e r i m e n t a l
products
was c o o l e d
the
the s o lv e n t
be o b s e r v e d .
rea ctio n
p o in t
were w e l l
not
of
have
has been d oc um ent ed
experim entation
may
of
the
As
U nder w a t e r - g a s
no t e m p e r a t u r e e f f e c t was o b s e r v e d .
ture e ffe c t
6.
Figure
the e x t r a c t i o n
in
d oc um ent ed
in
(22).
tem peratures
has
fo r
shown
no o b s e r v e d t e m p e r a t u r e e f f e c t .
to t h a t observed
tem perature
is
of
the
e xtract.
the s o l u b i l i t y
room t e m p e r a t u r e
the
re a ctio n .
32
32.00
Coal: C o l s t r i p Sub-bituminous
Solvent:
143 ml TMU, 7 ml HgO
pH: > 1 2 . 0
CO o v e r p r e s s u r e :
500 psi
24.00
16.00
X (15)
X (14)
X (16)
(17) X
X (2)
8.00
X (4)
A . OO
PERCENT EXTRACTION
♦Number i n d i c a t e s r u n number
.00
50.00
100.00
150.00
REACTION TEMPERATURE
Figure 6.
200.00
(C)
Temperature Dependence of Extr ac tion .
33
A dditiona l
lim it
of
the
mends
that
residue.
to
coal
a
tem perature
research
extract
soxhlet
be
should
used
these
e ffe ctive n e ss
of
products
e x tra c tio n
to
The a p p a r a t u s
achieve
be p e r f o r m e d
a ll
need
co n d itio n s.
the w ater-gas
the
using
remove
would
in
to
evaluate
solvent.
solvent
heated
be o p e r a t e d
Using
th is
s h ift
re a ctio n
s o lu b ility
The a u t h o r
c o a l-e x tra c t
to
the
to
the
reaction
m ate ria l
under
from
p a rtia l
system , a tr u e
r ec om­
the
vacuum
m e a su r e o f
the
can be d e t e r m i n e d .
Pressure E ffe c ts
■A s e r i e s
of
experim ents
was
r un
to
m o n o x i d e o v e r p r e s s u r e on t h e e x t r a c t i o n
s h ift
and
co n d itio n s.
the
pH o f
' In eac h
r un
the
solvent
was
greater
the
of
than
A p lo t o f
7.
author,
the
pressure
Appell
su rp rise
e ffe ct.
(22).
I OOO p s i g ,
This
but
his
would
a va ila b le
to
physical
mea su r e
th e re fo re ,
the
coal
co ncentratio n
was
or
not
the
and
the
e ffe cts
coal
contrary
at
The s o l v e n t
re s u lts
is
a
to
is
I 60°C
again
shown
in
pronounced
re s u lts
e ffe c t .for
carbon
under w ater-gas
was m a i n t a i n e d
12.
there
of
Figure
negative
document ed
pressures
was
up
to
by
about
t e m p e r a t u r e s w e r e n e a r 4 0 0 ° C.
thought
of
is
a p o s itiv e
increase
extent
it
re s u lt
re a ctio n
lim ita tio n s
the
the
He o b s e r v e d
I t was o r i g i n a l l y
pressure
of
the
C o ls trip
tem perature
143 ml o f TMU and 7 ml w a t e r .
To
assess
that
incre a sin g
co ncentratio n
h enc e l e a d
the
the
of
the
nascent
to gre a te r e x tra c tio n .
reactor
system,
rate
of
ju s t
po ssib le
to
determ ine
increases w ith
th e carbon monoxide o v e r ­
the
it
was
water-gas
if
the
not
hydrogen
Due t o t h e
possible
s h ift
nascent
pressure.
J
to
rea ctio n ;
hydrogen
34
24.00
Coal: C o ls t r i p Sub-bituminous
Solvent:
143 ml TMU, I ml HgO
pH: > 1 2 . 0
Reaction Temperature:
160°C
20.00
16.00
X (11)
12.00
X (17)
X (9)
a . OO
PERCENT EXTRACTION
♦Nu mber i n d i c a t e s r u n number
20.00
40.00
60.00
CO OVERPRESSURE
Figure 7•
80.00
(psi)
io o . oo
*
10'
Pressure Dependence of Ex trac tion.
35
A dditiona l
rate
of
the
research should
water-gas
d i o x i d e can e a s i l y
be p e r f o r m e d
s h ift
reaction..
be s e p a r a t e d
o d ic a lly
determ ining
monoxide
in
the
evaluate
Carbon
the
monoxide
extent
and
by gas c h r o m a t o g r a p h y m e t h o d s .
re la tiv e
th e va p o r phase,
to
amo un ts
of
both th e r a t e
carbon
of
carbon
By p e r i ­
d io xid e
and e x t e n t
and
and
carbon
re a ctio n
could
be m e a s u r e d .
The
species
is
negative
which
po ssib le
w ill
a lte rs
that
decrease
Formate
ion
w ater.
An
pressure
the
observed
e x tra c tio n
is
s o lu b ility
generated
increase
in
in
a
the
rea ctio n
the
e ffe ctive n e ss
due
to
the
the form ate
(22)
fa ct
may n o t
th a t
th is
i v n e s ti gat io n .
of
coal
in
any
the
and
ben ez e ne
e x tra c tio n s
It
tio n
A ppel I
His
and
in
in
the
the
carbon
the
It
solvent
solvent.
monoxide
form ate
so h i g h l y
solvent
the
co n d itio n s
He p e r f o r m e d
benzene.
chemical
and
ion
p o la r,
would
in
it
the
may be
be d e c r e a s e d
in
ion.
rea ctio n
degree.
p yrid in e
e x tra c tio n
as a c o a l
the
then
that
pressure
were d i f f e r e n t
s h ift
effect
than
those
hydrogenation
which d id n o t d i s s o l v e coal
extracted
re s u lts
not
negative
water-gas
presence o f a v e h i c l e o i l
app re cia b le
of
is
have e n c o u n t e r e d
his
of
bet ween
a
the s o lv e n t.
ion
e xtra ct
co ncentratio n
po ssib le
A ppel I
of
to
carbon monoxide o v e r p r e s s u r e would produce a
Because t h e TMU m o l e c u l e
the presence o f
due
form ate
coal
solvent m ix tu re .
its
be
c h a ra c te ris tic s
of
in
the
increase
that
may
increased c o n c e n tr a tio n s o f
the
corresponding
e ffe ct
were
of
a
the
coal
p rim a rily
one-step
residue
by
to
w ith
p yrid in e
and
hydrogenation
and
method.
is a ls o
po ssib le
that
a change
p r o d u c t s due t o a c h a ng e o f
in
rea ctio n
the
character
c o n d itio n s
is
of
the
e xtrac­
responsible f o r
36
the
negative
s o lu b ility
so lu b le
pressure
lim ite d ,
observed
of
250-1000
there
is
no c a r b o n
value f o r
pressure
in
the
coal
hydrogenation
co n d itio n s
that
products
prom ote
th e
are
most
show t h e g r e a t e s t o b s e r v e d e x t r a c t i o n .
psig
is
fo r
carbon
greater
monoxide o v e r p r e s s u r e
than
the
monoxide o v e r p r e s s u r e .
the coal
the
If
rea ctio n
e x tra c tio n
range
tio n
then
products w i l l
The
e ffe c t.
r e s e a r c h be d i r e c t e d
0-250 p s ig .
so t h a t
e xtra ctio n
Therefore,
sample sh o u ld e x i s t
range o f
observed
fo r
the
when
a maximum e x t r a c ­
a carbon
The a u t h o r
over
monoxide o v e r ­
recommends t h a t
future
th e optimum carbon monoxide o v e r p r e s s u r e
is
id e n tifie d .
pH E f f e c t s
It
proper
has
been
reported
reaction
proceed
reported
greater
at
any
to
is
su p e rio r
12.6.
pH v e r s u s
fin a l
solvent
runs
Col s t r i p
and
the
re a ctio n
As
can
performed a t
th is
fo r
the
(30).
best
reason,
water-gas
Basic
the
percent e x tr a c tio n
is
coal
used,
carbon
TMU and
w ater.
was
was
but
th is
a weak f u n c t i o n o f
seen
high
s h ift
obtained
pH o f
shown
pH.
from
Figure
is
is
low te m p e r a tu r e s
con d itio n s
re s u lts
percent e x tra c tio n
be
that at
the
r e a c t i o n was c l o s e l y m o n i t o r e d .
tem peratures,
is
the
researchers
pH v e r s u s
solvent
e x tra c tio n
rate
w ith
F or
b e f o r e and a f t e r t h e
solvent
e s se n tia l
appreciab le
be
th an
pH
by o t h e r
re a ctio n
are
when
not
generally
the
rea ctio n
pH
is
solvent
A p lo t o f o rig in a l
i n F i g u r e 8 , and a p l o t o f
shown
in
F i g u r e 3.
monoxide o v e r p r e s s u r e
The
to
runs
thought
was 500
encompassed
to
be
In a l l
a
p s i,
range
s ig n ific a n t
of
since
tem perature.
8 , most o f
the
experim ental
One r u n was p e r f o r m e d u n d e r a c i d i c
runs
condition s
were
and
28.00
37
Coal: C o l s t r i p Sub-bituminous
Solvent:
143 ml TMU, 7 ml HgO
CO O v e r p r e s s u r e :
500 psi
Temperature: 25-205°C
& (3)
24.00
20.00
(15)
16.00
(14)
12.00
PERCENT EXTRACTION
♦Nu mber i n d i c a t e s r u n number
0.00
(2 )X
X (7)
> (4)
4.00
8.00
ORIGINAL
Figure 8.
: (16)
'(17)
12.00
16.00
SOLVENT pH
pH of Solvent Before Reaction Versus Observed Extraction.
30. OO
38
C o a l: C o l s t r i p Sub-bituminous
Solvent:
143 ml TMU, 7 ml H2O
CO O v e r p r e s s u r e :
500 p s ig
Temperature: 25-205°C
25.00
20.00
X (15)
{4
15.00
PERCENT EXTRACTION
♦Number i n d i c a t e s r u n number
X(17)
(4 )X
10.00
(7)X
X (16)
4.00
6.00
FINAL
Figure 9•
8.00
10.00
12.00
SOLVENT pH
pH of Solvent A ft er Extraction Versus Observed Extraction.
39
was o n l y
m a rg in a lly
e xtra ctio n
than
may
12.6
to
e xtra ctio n
rea ctio n
the
13.0.
was
spe cu la tive ,
d ra m a tica lly
when
pH o f
(23)
observed
upon
e x is ts
Although
Ross
was g r e a t e r
Based
la tio n
ris e
su cce ssfu l.
when
of
general ,
if
fin a l
solvent
pH.
esting
lig h t
of
fa ct
bet ween o r i g i n a l
is
may be
p o ssib le
re la te d .
th e s is ,
the
in
w ill
the
lower
s o lu b ility
As
the
Because o f
one
run
the c o a l.
th en
run
the
was
3,
Figure
that
whereby
rea ctio n
the
that
a pronounced
pH
it
fo r
the
is g re a te r
increase
w ater-gas
In
s h ift
appears t h a t a rough c o r r e ­
solvent
that
and
the
e x tra c tio n
fin d s
there
The
me th od s
in
th is
was
o nly
e x tra c tio n
increases
observation
a
weak
of
w ith
in te r­
co rre la tio n
and t h e n e g a t i v e p r e s s u r e e f f e c t
the
solvent
in
pressure
b u ffe rin g
where
that
if
remain
is
section
of
th is
may
d ic ta te
the
coal
the
form ate
ion
con ce n tra tio n
h enc e
could
effe ct
s o lid
possibly
e xtra ct
lower
the
of
s o di u m
the
coal
hydroxide
in
was
the reac­
added
to
enough s odi um h y d r o x i d e w e r e p r e s e n t ,
high
by t h e
re s u lt
of
and
e ffe cts
the re sid u e .
apparent
pH
the
pH e f f e c t
represented
researchers
re a ctio n .
the
pH w o u l d
9.
pH o f
Increasing
performed
is
9,
concentratio n
extract
the
solvent
in
ion
I t was b e l i e v e d
number
shown
the
so lve n t.
o f coal
Figure
The a u t h o r
p ostulate d
pH o f
solvent
that
pH and e x t r a c t i o n .
that
form ate
s o lu b ility
tio n ,
the
solvent
so lve n t
appears
increasing
It
the
that
the
appears
12. 6 .
than
exam ination
In
in
d oc um en te d
bet ween t h e f i n a l
co a l.
the
it
of
during
highest
th is
running
m aintained
the
at
run
the
observed
would
reaction
a
re a ctio n .
high
This
e xtra ctio n
in d ic a te
should
level
to
be
run,
value
fu tu re
analyzed
throughout
the
40
One r u n ,
instead
of
r un
number
sodium
hydroxide
O bs er v ed e x t r a c t i o n
was
s ig n ific a n tly
tio n s .
This
pH o f
10.2
that
th is
tio n
rate.
the
lower
is
was
than
of
used
to
A d d itio n a l
fo r
of
in
lig h t
should
correspond
carbonate
research
coal
in
pH o f
on
to
a
be
fa ct
that
re la tiv e ly
solvent
carbon
performed
can
c o rre la tio n
a r e shown
be
seen
bet ween
in
from
the
was
to
performed
re s u lts
and w i t h
A ppel I
( 2 2)
in
chemical,
which
method.
under
to
Figure
of
and Takemura
were
r un
a solvent
evaluate
water-gas
and
at
s h ift
Bakerstown
143 ml
16 0 ° C ,
pH g r e a t e r
the
TMU and
500
than
psi
12.6.
10.
10,
there
coal
r a n k c o a l s ' a p p e a r t o be s o l u b i l i z e d
coals.
fin a l
extrac­
id e n tify
sub-bitum inous,
experim ents
Figure
rank
its
solvent e x tra c tio n
runs
Col s t r i p
Al I
monoxide o v e r p r e s s u r e ,
The r e s u l t s
As
run.
high
or
b i t u m i n o u s c o a l s w e r e u s e d ; t h e s o l v e n t was
each
the
i s due t o d i f f e r e n c e s
h ig h -v o la tile
fo r
which
based upon F i g u r e 9,
Savage
water
solvent.
13 p e r c e n t ,
co n d itio n s.
7 ml
the
Rank E f f e c t s
e xtra c tio n
lig n ite ,
the
p re d ic t,
the
s h ift
experim ental
rank
of
re s u lt
should
the water-gas
three
the
sodium c a r b o n a te
s o d i u m h y d r o x i d e u n d e r t h e same c o n d i ­
One w o u l d
Coal
A series
where
adjust
high.
sodium
bas es w o r k b e s t u s i n g
of
performed
is u n c e r ta in whether t h i s
s o lu b ility
e ffe ct
also
in te re s tin g
pH v a l u e
It
was
t h e s o d i u m c a r b o n a t e was o n l y
re la tiv e ly
high
character.
w ith
re s u lt
is
20,
and
appears
th e
to ta l
to
be a s i g n i f i c a n t
d is s o lu tio n .
to a g r e a t e r degree than
( 2 4)
hav e a l s o doc ument ed
c o a l s a r e more r e a c t i v e u n d e r w a t e r - g a s
s h ift
co n d itio n s.
higher
that
Low
rank
low ra n k
(21 )- - S a v a g e l i g n i t e
I ( ( I T ) - - C o l s t r i p sub-bituminous
12.00
16.00
20.00
X
X (S )--B a k e rs to w n highv o l a t i l e bituminous
.00
PERCENT EXTRACTION
24.00
41
*70.00
75.00
80.00
PERCENT C I N
Figure 10
Initial
85.00
90.00
COAL
Carbon Content Versus Observed Extraction.
42
Researchers
g e n e ra lly
w orking
report
that
on
coal
the best
e x tra c tio n
re s u lts
using
solvents
are observed w it h
alone
b itu m in o u s coal
(17).
Coals
hydrogen
e nc e
in
low
rank
than c o a l s o f
a ttack
and e t h e r
coal
of
linkages
rank
presence
site s
and
of
are
higher
or
rank.
the
observed
mor e
This
fu n ctio n a l
being
nascent
a pparen tly
lends
a ttack
is
due
the coal
candidates.
e x tra c tio n
attacked
no d o u b t
groups w i t h i n
prime
hydrogen
re a d ily
to
a d iffe r­
m a trix,
The c o r r e l a t i o n
c re d ib le
under
by n a s c e n t
the
evidence
condition s
used
ester
bet ween
to
in
the
th is
e xperim ent.
Solvent
When
retained
in
bet ween
the
was
the
the
coal
versus
it
observed
residue,
observed
residue.
solvent
that
it
a
Figure
re te n tio n
11,
fo r
t e m p e r a t u r e and s o l v e n t
considered
a
chemisorbed
on
nature
w ith
of
the
increased
expected
if
sp e c ific
the
coal
surface
carbon
that
so lve n t,
at
of
e x tra c tio n .
room
the
of
coal.
s p e c ific
residue
A c h ange
in
the s u rfa ce c h a r a c t e r is t ic s
of
case
in
is
p lo tte d
the
solvent
was
s o lv e n ts ,
amount
of
the
A pparen tly
does
the
may e x i s t
500
psi.
co nsiderab ly.
tem perature.
coal
was
retained
e x tra c tio n
overpressure
c e rta in
solvent
so lve n t
In eac h
pH v a r i e d
a
of
a c o rre la tio n
amount o f
monoxide
fo r
amount
that
amount
C o ls trip
The r e a c t i o n
states
the
the
w ater,
( 1 7)
the
and
was TMU and
Dr yden
and
s ig n ific a n t
was p o s t u l a t e d
e xtra ctio n
In
R etention
not
solvent
th e coal
change
and
TMU
is
solvent
is
the
a p preciab ly
re te n tio n
changed.
chemical
would
be
43
32. OO
Coal: C o l s t r i p sub-bituminous
Solvent:
TMU/HgO
CO O v e r p r e s s u r e : 5 0 0 p s i
24.00
16.00
X
xd )
X (16)
(2)X
(4) X
8.00
(ID
X(7)
(9)>d
.00
PERCENT EXTRACTION
♦Nu mber i n d i c a t e s r u n number
0Or OS
o!
10
o'. 15
o/ 20
SOLVENT RETENTION g / g
Figure 11.
0. 25
residue
Solvent Retention Versus Ex trac tion.
The
solvent
reader
should
re te n tio n
note
can
that
probably
a c e rta in
be a t t r i b u t e d
Each r e s i d u e was washed w i t h a c e t o n e u n t i l
filte r-c a k e
and
it
is
appeared
known
c o lo rle ss.
that
some
amount
were
v a ria tio n
to experim ental
the e f f l u e n t
The c o l o r l e s s
residues
of
in
th e
technique.
from the
residue
e n d p o i n t was s u b j e c t i v e ,
washed
w ith
co nsiderab ly
more
acetone than o t h e r s .
The v i a b i l i t y
in
grave
from
the
the
jeo p a rd y
residue
cost
the w ater-gas
unless
or
associated
mus t be r e c o v e r e d
c a lly
of
w ith
these
the
coal
Researchers
water-gas
S h ift
fe a s ib le .
The
solvent
author
the s o lv e n t are very
T hese
ensure
or
that
m entation
id e n tify
the
had
research work.
reaction
were
areas
i n A p p e n d i x A.
the
r emove
is
is
solvent
Because
of
a ll
of
the
process
to
be e c o n o m i ­
s ig n ific a n t
chances
the
e x tra c tio n .
th e
th is
process
to
problem
become
fo r
solvent
if
the
com m ercially
com plete
recovery
of
Experim entation
data
that
performed
chance
w ith
of
a r e shown
that
other
fo r
parameters
The r e s u l t s
con d itio n s
fo r
m et hod
performed
reasonable
subject
solve
that
were
re a ctio n
a
the
to
s o lv e n ts , v ir t u a lly
e xtra ctio n
s u b sta n tia te
experim ents
e x tra c tio n
si im.
experim ents
hypothesis
increase
mus t
fe e ls
solvent
be d e v i s e d
residue
A dditiona l
Some
can
d ra m a tic a lly
from
fe a s ib le .
met hods
s h ift
t wo
were
designed
researchers
reasons.
and c o n d i t i o n s
fo r
success
and
adequate, p o t e n t i a l
these e x p e rim e n ta l
in T a b le 7 , w i t h
to
hav e
The
used
the
to
th is
second
ju s tify
a
presented.
firs t
in
test
was
to
e xp e ri­
was
to
a d d itio n a l
r u n s and t h e p e r t i n e n t
sp e cific, con d itio n s
given
45
E xtraction
T a b l e 7•
R esults
fo r
Run No.
Solvent
Wei g h t %
E xtra ctio n
12
TMU/Tetralin/HMPA/HgO
35
13
t m u / h m p a / h2 o
23
19
T M U / T e t r a l InZH2 O
20
15
TMUZH2 O Z a d d i t i o n a l
17
TMUZH2 O ( n o r m a l
18
TMUZH2 OZh 2 o v e r p r e s s u r e
To h e l p d e t e r m i n e
ant
ro le
in
performed
monoxide
less
run
of
if
e x tra c tio n
overpressure.
18 a r e
s h ift
Ward
evidence
coal
( 2)
could
d oc um ent ed
is
greatest
nascent
more
re a ctive
12,
one
in
place
r un
not
18,
of
im port­
formed
was
carbon
s u b s ta n tia lly
than
co n clu sive ,
hydrogenation
an
experim ent
overpressure
hydrogen
in
substantia l
when
a
e x tra c tio n
evidence
m ixtu re
value
the
via
of
fo r
any
re su lts
th e w a t e r -
C o ls trip
the observed
t h a t enh an c ed c o a l
of
solvents
was
f o r a r un u s i n g
The a u t h o r
s o l v e n t s may a l s o w o r k u n d e r w a t e r - g a s
r un
used
plays
sub-
hydrogen.
t u r e o f TMU, HMPA, and t e t r a l i n .
Table 7 f o r
re a ctio n
7 fo r
W hile
the
observed
was
hydrogen
used.
11
coal ,
Table
that
presented
his
in
under
than elem ental
be
C o ls trip
shown
m o n o x i d e was
rea ctio n
bitum inous
As
19
17
s h ift
overpressure
was o b s e r v e d
carbon
of
H2 O
run)
the w ater-gas
hydrogen
e xtra ctio n
run
tio n
the
where
where
gas
of
E x p e riments.
In d ivid u a liz e d
surmised
s h ift
e x tra c tio n
used.
He
a solvent m ix­
that
th is
co n d itio n s.
was q u i t e
extrac­
high.
m ixture
As shown
in
In f a c t ,
46
th is
was
the
th is
in v e s tig a tio n .
Runs
highest
13 and 19 w e r e a l s o
r un
13,
was
s ig n ific a n tly
a m ixture
so lve n t.
In
of
r un
a
19,
so lve n t.
It
c o n d itio n s
One
present
r un
in
water-gas
than, i f
a
w ith
the
m ixture
n or ma l
appears
in
the
TMU,
TMU and
run
17,
t e t r a l in
greater
if
course
of
so lve n ts.
In
and t h e o b s e r v e d e x t r a c t i o n
t h an
chos en
if
were
was
ju s t
p ro p e rly,
the e x t r a c t io n
performed
m ixture
re a ctio n .
In
In r un
to
when
a ll
s a tis fy
other
o f coal
c o n d itio n s,
a d d itio n a l
if
used
used
as
and
a
the
TMU w e r e used
a
m ixture
of
under water-gas
for
was
r un
adequate
water
requirem ents
7 .5 ml
of
w ater
was
fo r
the
was used
7 •5 ml o f w a t e r was added t o
w a t e r was a l i m i t i n g
t h e n an
water
if
the
runs,
1 5 , an a d d i t i o n a l
in th e s o l v e n t
value.
determ ine
to
I t was t h o u g h t t h a t
w ater present
e xtra ctio n
of
th a t,
solvent
experim ental
be o b s e r v e d
ju s t
was o n l y s l i g h t l y
also
the s o lv e n t.
the s o lv e n t.
during
t h a n any one s o l v e n t a l o n e .
was
s h ift
doc ument ed
performed using a m ix tu r e o f
s o l v e n t s may be more e f f e c t i v e
s h ift
value
TMU and HMPA was u s e d ,
b e tte r
observed e x t r a c t i o n
as
e xtra ctio n
increase
added.
in
r e a c t a n t under
the e x t r a c t io n
The a d d i t i o n a l
7•5
would
ml
of
15 had no s i g n i f i c a n t e f f e c t on t h e
47
SUMMARY AND CONCLUSIONS
1.
The l a r g e s t e x t r a c t i o n
35 p e r c e n t .
was
used
in
HMPA, 50 ml
2.
observed f o r
Col s t r i p
To a c h i e v e
th is
re s u lt,
con ju n ctio n
w ith
a solvent
s u b -b itu m in o u s coal
water-gas
m ixture
s h ift
of
was
hydrogenation
50 ml
TMU, 50 ml
t e t r a l i n , and 5 ml w a t e r on 4 . 9 2 g o f c o a l .
Solvent
e xtra ctio n
under
water-gas
solvent
e xtra c tio n
alone
or
s h ift
solvent
co n d itio n s
e x tra c tio n
is
in
greater
the
than
presence
of
hydrogen o v e r p r e s s u r e .
3.
There
appears
rea ctio n
to
be no
solvent
d e nc e e x i s t s
tem perature
e xtra ctio n
that
in
s o lu b ility
e ffe ct
the
fo r
the
water-gas
r a n g e o f 25 t o 2 0 0 ° C .
lim its
of
coal
e xtra ct
in
s h ift
Some e v i ­
the
solvent
may have masked a t e m p e r a t u r e e f f e c t ,
4.
T h e r e a p p e a r s t o be a n e g a t i v e
tiv e
to
p sig .
carbon
monoxide
However,
the c o n d itio n s
5.
6.
th is
e x is ts
e x tra c tio n .
As
the
e xtra ctio n
also
be g r e a t e r
than about
is
encountered
of
the
may be an
bet ween
in
a rtifa c t
th is
re s id u e could
the
fin a l
increases.
retained
in
overpressure
effect
the
from
fo r
e x tra c tio n
range
of
chemical
re la ­
250 t o
1000
form ation
fo r
In t h e s e e x p e r i m e n t s .
A c o rre la tio n
Solvent
pressure
fin a l
solvent.
It
solvent
pH
appears
pH and
increases,
that
in itia l
the
the
coal
residue.
exp e rim e n ta tio n ,
be a t t r i b u t e d
to
6 to
For
pH must
to occur.
the
17 p e r c e n t
incorporated
observed
solvent
12. 6 f o r s i g n i f i c a n t e x t r a c t i o n
in
the observed
of
co n d itio n s
the w eight
so lve n t.
48
7.
Lower
rank
co a ls
solvent e x tra c tio n
8.
are
more
e a s ily
c o n d itio n s
extracted
than h i g h e r
Compounds o t h e r
than w a te r are v o l a t i l i z e d
associated w ith
the d ry in g o f c o a l.
under
water-gas
s h ift
rank c o a ls .
under c o n d i t i o n s
norm ally
49
RECOMMENDATIONS FOR FUTURE RESEARCH
1.
Tests
should
gas s h i f t
be
r un
rea ctio n
to
fo r
determ ine
the
the
c o n d itio n s
extent
and
e mp l o ye d
in
rate
of
th is
the w a te r-
experim enta­
tio n .
2.
3.
An e f f o r t
and
c la rify
if
the s o lv e n t
v a lid .
it
is
the
M u ltip le
Tests
Tests
th e ir
that
should
s o lu b ility
chemical
nature.
assumptions
th is
be
experim ents
lim ita tio n s
r un
be
d ryin g o f c o a l.
run
used
products
from th e
T h is would h e lp to
in
th is
study
are
is experim ental Iy v e ry d i f f i c u l t .
bases used t o c o n t r o l
t h e pH
be e v a l u a t e d .
to
to
should
control
evaluate
t h a t maximize coal
should
the e x t r a c t io n
e ffe ctive n e ss of d if fe r e n t
e x tra c tio n
should
is o la te
re te n tio n
recognized
re a ctio n
con d itio n s
6.
ch a ra cte rize
The r e l a t i v e
solvent
5.
be made t o
solvent
of
4.
should
the
be
run
to
the e x te n t o f
carbon
determ ine
the
monoxide
if
re a ctio n .
overpressure
e x tra c tio n .
ch a ra cte rize
the
off-gas
products
from
the
50
REFERENCES CITED
51
REFERENCES CITED
1.
Sears, J .T .,
Proposal f o r
2.
War d, T . L . , " T h e A c t i o n o f T e t r a m e t h y l u r e a and H e x a m e t h y I p h o s p h o r a mi de B l e n d e d w i t h O t h e r S o l v e n t s on t h e D i s s o l u t i o n o f C o a l , " M.S.
T h e s i s , Mont ana s t a t e U n i v e r s i t y , Bozeman, M o n t a n a , 1984.
3.
I c h i o k a , I . , " T h e E f f e c t o f T e t r a m e t h y l u r e a and H e x a m e t h y I p h o s p h o r a m i d e on t h e D i s s o l u t i o n o f C o a l , " M.S. T h e s i s , Mont ana S t a t e
U n i v e r s i t y , Bozeman , M o n t a n a , 1985.
4.
B a l t i s b e r g e r , R . J . e t a l . , " C a r b o n M o n o x i d e - W a t e r v s . H ydr ogen f o r
L iq u e fa ctio n :
The R e d u c t i o n o f D i p h e n y l s u l f i d e , T h i o a n i s o l e and
D i b e n z o t h i o p h e n e , " Am. Chem. Soc. D i v . Fuel Chem. P r e p r i n t s , v o l . 2 4
(2),
p.74,
" C o a l C o n v e r s i o n T h r o u g h E x t r a c t i o n by S u p e r s o l v e n t s
D . O . E . G r a n t No. DE- FG22- 82PC50 787, 1982.
(1979).
5.
R os s, D. S. e t a l . , " C o n v e r s i o n o f B i t u m i n o u s
Systems," F u e l, v o l. 6 3 , p.1206, (1984).
Coal
in
COZH2 O
6.
Takem ura, Y . e t a l . , " C a t a l y t i c L i q u e f a c t i o n o f V a r i o u s Coals Using
a M i x t u r e o f Carbon M o n o x i d e and W a t e r , " Fuel , v o l . 6 2 , p.-l 133,
(1983).
7.
Sears,
8.
W h i t e h u r s t , D. D. e t a l . ,
Y o r k , New Y o r k , 1980.
9.
Meyers,
York,
10.
11.
12.
R. A.
P rivate
et a l.,
Communication,
Coal
Coal
1985-
L i q u e f a c t i o n , A c a de m i c P r e s s ,
Handbook, Marcel
Decker,
New Y o r k ,
New
New
1981.
S t a c h , E. e t a I . ,
■ S t u t t g a r t , 1982.
Coal
P e t r o l o g y , Gebruder B o r n t r a e g e r , B e r l i n ,
B o u s k a , V.
Geochemistry o f C o a l, E l s e v i e r S c i e n t i f i c
Company, A m st er d a m, O x f o r d , New Y o r k , 1981.
Meyers,
York,
13.
J.T .,
R. A.
et a l.,
Coal
S t r u c t u r e , A c a de mi c P r e s s ,
P ublishing
New Y o r k ,
New
1982.
L a r s o n , R. A. e t a I . , O r g a n i c C h e m i s t r y o f
S o c i e t y , C h i c a g o , I l l i n o i s , 1978.
C o a l , American
Chemi cal
52
14.
G o r b a t y , M . L. e t a l . ,
Y o r k , New Y o r k , 1982.
15.
S h i n n , J . H . , " F r o m Coal t o S i n g l e - S t a g e and T w o - S t a g e P r o d u c t s :
R e a c t i v e Model o f Coal S t r u c t u r e F u e l , v o l . 6 3 , p . 1 1 8 7 , ( 1 9 8 4 ) .
16.
van Bodegom, B . e t a l . , " A c t i o n ,of S o l v e n t s on Coal
t u r e s , " F u e l, v o l. 6 3 , p-346, (1984).
17.
D r y d e n , I . G . C . , " S o l v e n t Power f o r C o a l s a t Room T e m p e r a t u r e , "
C h e m i s t r y and I n d u s t r y , v o l . 3 0 , p . 5 0 2 , ( 1 9 5 2 ) .
18.
van K r e v e l e n , D . W . , " C h e m i c a l S t r u c t u r e and P r o p e r t i e s o f Coal
XXVI I I - C o a l C o n s t i t u t i o n and S o l v e n t E x t r a c t i o n , " F u e l , v o l . 4 4,
p.229,
Coal
Science,
Vol ume I , A c a de m i c P r e s s , New
at
A
Low Te mp er a ­
(1965).
19.
Hombach, H. P . , " G e n e r a l
p.465, (1980).
Aspects o f
Coal
S o lu b ility ,"
2 0.
N o r m a n t , H . , " H e x a m e t h y I p h o s p h o r a m i d e , " Angew.
E d i t . , v o l . 6 , p . 1046, ( 1 9 6 7 ) .
21.
L u t t r i n g h a u s , A.
R e a g e n t , " Angew.
22.
A ppel I , H. R. e t a l . , " S o l u b i l i z a t i o n o f Low Rank Coal w i t h Carbon
M o n o x i d e and W a t e r , " Chem. I n d . ( L o n d o n ) , v o l . 4 7 , P - 1 7 0 3 , ( 1 9 6 9 ) .
2 3.
R os s, D. S . e t a l . , " C o n v e r s i o n o f B i t u m i n o u s
S y s t e m s , " F u e l , v o l . 6 3 , p. 120. 6, ( 1 9 8 4 ) .
24.
Takem ura, Y . e t a l . , " C a t a l y t i c L i q u e f a c t i o n o f V a r i o u s Coals Using
a M i x t u r e o f Carbon M o n o x i d e and W a t e r , " Fuel , v o l . 6 2 , p . 113 3,
Chem.
Fuel , v o l . 5 9,
Inte rn a t.
e t a l . , " T e t r a m e t h y l u r e a as a S o l v e n t and '
Chem. I n t e r n a t . E d i t . , v o l . 3 , p . 2 6 0 , ( 1 9 6 4 ) .
Coal
in
CO/H^O
( 19 83 ) .
25.
S m i t h , J . M. , Van N es s , H . D . ,
T h e r m o d y n a m i c s , McGraw H i l l ,
26.
E l l i o t t , D. C. , S e a l o c k J r . , L . J . , " U s e o f Aqueous C a t a l y t i c
P r o c e s s i n g f o r W a t e r - G a s S h i f t C o n v e r s i o n , " Am. Chem. Soc. D i v .
Fuel Chem. P r e p r i n t s , v o l . 2 9 ( 6 ) , p . 14 , ( 1 9 8 4 ) .
27.
J o n e s , D. e t a l . , " C a r b o n M o n o x i d e - H y d r o g e n - W a t e r :
Reduction o f
B e n z o p h e n o n e , D i p h e n y l c a r b i n o l , and D l p h e n y l m e t h a n e , " J . Or g.
C h e m. , v o l . 4 3 ,
2 8.
P • 17 5 ,
I n t r o d u c t i o n t o C hem ic al E n g i n e e r i n g
New Y o r k , New Y o r k , 1959.
(1978).
B a l t i s b e r g e r , R . J . e t a l . , " C a r b o n M o n o x i d e - W a t e r v s . H y dr ogen f o r
L iq u e fa ctio n :
The r e d u c t i o n o f D i p h e n y l s u l f i d e , T h i o a n ! s o l e , and
D i b e n z o t h i 0 p h e n e , " Am. Chem. S o c . D i v . Fuel Chem. P r e p r i n t s ,
v o l . 2 4 (2 ), p .74, (1979).
^
53
29•
'30.
31.
M o n d r a g o n , F . , Ouchi , K . , " C o a l
G e n e r a tio n 2.
Z i n c - W a t e r Model
P-973, (1984). ,
L i q u e f a c t i o n , by I n - S i t u Hy dr ogen
Compound R o g e t i o n t Fuel , v o l . 6 3 ,
'
L y n c h , I.. J . e t a l . , " I r o n C a r b o n y l C a t a l y z e d R e d u c t i o n s o f Model
Coal C o n s t i t u e n t s Under W a t e r - G a s S h i f t C o n d i t i o n s , " Am. Chem. S o c .
D i v . Fuel Chem. P r e p r i n t s , v o l . 2 ( 1 ) , p . 1 7 2 , ( 1 9 8 3 ) .
M i c k l e y , H. S. e t a l . , A p p l i e d M a t h e m a t i c s
M c G r a w - H i l l , New Y o r k , New Y o r k , I 9 5 7.
i n C he m i c a l
E ng in e e rin g ,
APPENDICES
55
APPENDIX A
RAW DATA FROM. EXTRACTION EXPERIMENTS
Table 8.
Experimental
Conditions for Each Extraction Run.
Temperature
( 0 C)
pH B e f o r e
pH A f t e r
600
167- 5
13-30
7-72
480
59.0
12. 02
9.00
500
1 6 9. 5
-14
I 1.74
TMUZH2 O
490
177- 0
13. 62
8.54
Col s t r i p
TMUZH2 O
550
1 6 1. 5
6 .8 9
8.70
7
Col s t r i p
TMUZH2 OZHCl
500
158.0
NZA
7.60
8
Bakerstown
TMUZH2 O
500
157.0
1 2. 78
7-75
9
Col s t r i p
TMUZH2 O
1000
150.0
12. 78
9.05
11
Col s t r i p
TMUZH2 O
250
1 58 . 5
12. 92
9.64
12
C o ls trip
TMUZHMPAZTETZH2 O
500
1 62 . 0
13.12
1 0 . 67
13
C o ls trip
TMUZHMPAZH2 O
500
160.0
—14
1 1.01
14
C o ls trip
TMUZH2 O
500
25.0
12. 44
9-40
15
C o ls trip
TMUZH2 OZad.
O
O
LA
157- 5
13-46
1 0. 27
Run
No.
Coal
1
Col s t r i p
TMUZH2 O
2
C o ls trip
TMUZH2 O
3
Col s t r i p
TMUZH2 O a d .
4
Col s t r i p
6
Pressure
(psig)
S olvent
NaOH
HgO
Table 8 - - c o n t inued.
Temperature
(°c)
pH B e f o r e
pH A f t e r
500
205.5
13.68
11 . 2 7
TMUZH2 O
500
153.0
13.69
9.65
C o ls trip
TMUZH2 O
SOO(H2 )
158.0
12.53
9.98
19
Col s t r i p
TMUZTETZH2 O
500
158.5
12.46
9.22
20
Col s t r i p
TMUZH2 OZNaCO3
500
157-5
12.89
10.21
21
Sav. L i g .
TMUZH2 O
500
152.5
13.43
11.00
Run
No.
Coal
16
C o ls trip
TMUZH2 O
17
Col s t r i p
18
Solvent
Pressure
(psig)
Table 9•
Run
No.
Raw Data for Experimental
I n i t i a l W t.
Coal (g)
Extraction Runs.
Final Wt.
R e s i d u e ( g)
Elemental
Ni t r o g e n
A n a l y s i s R e s i due
Carbon
Hydr ogen
% Ash
R es idue
I
4.8848
2.8 216
1.88
66.07
4.80
10. 55
2
5.0654
3.8890
1.82
66.90
4.92
9 - 54
3
5.0680
3.2118
I . 26
64.60
4. 51
11. 26
4
5.0219
4.0324
1. 85
67. 21
4.65
10.22
6
4.9910
3.8205
4.27
66.86
5.40
10.42
7
4. 9051
3. 9721
1 . 97
63.02
4.64
10. 17
8
5-2574
4.8 928
1. 75
75.05
4.76
10.21
9
5.0043
4.1 049
1. 83
65.12
4.69
9-59
11
4.9893
3-7349
2.02
64.88
4.80
9 - 87
12
4.9 190
3.4738
363
64.60
5.27
12. 04
13
4.7062
3-8941
4.27
62.18
5.27
13-93
14
5-5857
4.9807
3.53
64.97
5-29
10. 26
15
5.7302
4.2123
1. 93
66.66
4.82
10.06
Table 9- - co n tinued.
Run
No.
I n i t i a l W t.
Coal (g)
Elemental
A n a l ys i s R e s ! d u e
Final W t.
R e s i d u e ( g)
N itrogen
Carbon
Hydr ogen
% Ash
R es !due
16
5.8376
4.6545
2.36
65-51
4.63
9-97
17
5.3344
4.0886
I . 85
6 6. 2 2
4.76
10.61
18
5. 2971
4.2758
1.86
6 7 - 83
4.92
9-60
19
5.2327
3.6494
1 . 54
67.16
4.92
9.68
20
4.9143
3. 8501
I . 94
67.23
5.06
9-75
21
4.8204
3.4953
3-70
64.18
4.57
8.65
Table 10.
Chemical Analysis of Coal Used in Experimentation.
Elemental
Ni t r o g e n
Coal
A nalysis
Ca r bon
(%)
Hydr ogen
% Ash
% Water
Content
C ontent
C o ls trip
(wet)
0.92
56.67
4.48
8.04
Col s t r i p
(dry)
1. 13
67.55
4.58
N/A
Savage L i g n i t e
(wet)
1 . 07
52. 01
3-35
6.50
Savage L i g n i t e
(dry)
1- 35
65.58
3-85
N/A
1. 62
77.49
4.86
10. 25
Bakerstown
(wet)
1 7. 80
0.0
27.96
0.0
0.27
61
I
APPENDIX B
SAMPLE CALCULATION
62
SAMPLE CALCULATION
T h i s a p p e n d i x shows t h e c a l c u l a t i o n
Needed e x p e r i m e n t a l
run
13-
data:
S olvent:
68 ml
C o ls trip
sequence f o r
co a l:
Residue:
TMU, 75 ml
HMPA
i n i t i a l wt
4.7062 g
mass f r H2 O 0 . 178
mass f r ash
0.0804
e l e m e n t a l a n a l y s i s ( d r y , ash c o n t a i n i n g )
N 1.13%
C 67. 55%
H 4.58%
w e i g h t 3*8941 g
mass f r H2 O . 0242
mass f r ash
. I 393
e l e m e n t a l a n a l y s i s ( w e t , ash c o n t a i n i n g )
N 4.28%
C 62.18%
H 5.27%
C a lc u la te elemental
w a te r-fre e b a s is .
ana l y s i s
W ater-Free
Weight
Element
of
coal
Ash
C o r r e c t i on
organic
m atter
on
an
ash
Corrected
Weight
% Organic
Ash S W a t e r - F r e e
N itrogen
0.0093
0.0093
1 . 25
Carbon
0.5553
0.5553
74.88
Hydr ogen
0.0377
0.0377
5.08
Ash
0.0804
Oxygen
Total
- 0 . 0-
- 0 . 0-
0.1393
0.1393
1 8 . 78
0.8 220
0.7416
99* 99
-0.0804
Next the r e s i d u e a n a l y s i s
is c a l c u l a t e d
on a d r y ,
Assume t h a t m a t e r i a l v o l a t i l i z e d a t I 03°C i s w a t e r .
H yd r o ge n
Oxygen
l o s s due t o w a t e r = . 0 2 4 2 " ( 2 g H / l 8 g H 2 0 )
l o s s due t o w a t e r = . 0 21 59
and
-
ash-free
.00279
basis.
63
% Ash &
W ater-Free
Corrected
Weight
C o r r e c t ion
Weight
Element
Wet
Ana l y s i s
N itrogen
0.0428
0.0428
5.12
Carbon
0.6 218
0.6218
74.33
Hydr ogen
0.0527
-0.0027
0.0500
5.98
Ash
0.1393
-0.1393
-0.0-
-0.0-
Oxygen
0.1434
-0.0215
0.1219
14. 57
Tota I
I . 0 000
0.8365
1 00 . 0 0
A d j u s t e l e m e n t a l a n a l y s i s by r e m o v i n g s o l v e n t m o l e c u l e s u n t i l
gen c o n c e n t r a t i o n i s t h e same as t h e o r i g i n a l c o a l ( 1 . 2 5 ) .
Assume t h a t s o l v e n t i s r e t a i n e d
as i n t h e b u l k s o l v e n t .
Assume t h a t
the
s o l v e n t m o l e c u l e s do n o t
68 ml TMU *
78 ml
in
HMPA *
mass f r a c t i o n
C
fo r
N
15.91
9.07
HMPA
7-73
30.93
1 8. 0 4
20.19
Total
14.59
64.99
33.95
29-26
0.1022
0. 45 51
0.2378
0.2 049
Set up f o u r mass b a l a n c e e q u a t i o n s and a c o n s t r a i n t
f i n a l n i t r o g e n c o n c e n t r a t i o n i s e q u a l t o 1.25%.
total
to ta l
total
total
total
ra tio
O
34.06
=
=
=
=
=
same m o l a r
so lve n t.
6.86
H
C
0
N
S
the
fragm ent.
TMU
MF
in
. 9 68 7g TMU/ml = 6 5 .8 79 TMU
1 . 0 2 5 3 9 HMPA/ml = 7 6 . 9 0 g HMPA
C a lc u la te elemental
H
residue
the n i t r o ­
weight
w eight
weight
w eight
w eight
o f hydrogen
o f carbon in
o f o x y ge n i n
o f n itro g e n
o f solvent
14 2 . 79g t o t a l
I .000 t o t a l
equation
in c o r r e c t e d r e s id u e
c o rre c te d residue
c o rre c te d residue
in c o r r e c t e d r e s id u e
so t h a t
the
64
The e q u a t i o n s a r e :
H
C
0
N
=
=
=
=
. 0512
.7433
. 1457
. 0 5 12
- S ( . I 022)
- S(.4551)
- S(.2049)
- $(.2378)
N / (H+C+O+N) = . 0125
Sim ultaneous
H
C
0
N
=
=
=
=
so lu tio n
of
t h e above e q u a t i o n s
y ie ld s :
. 0 422
.6651
.1105
. 0104
. 8 2 82
(solvent
The a bov e r e s u l t s
y ie ld
ret
fa cto r)
a corrected
r e s id u e elem ental
a n a lysis:
H=
5.10%
C = 8 0 . 31%
0 = 13.34%
N =
1.25% ( t h e v a l u e e x p e c t e d )
A l l o f the in fo r m a tio n f o r c a l c u l a t i n g the
E q u a t i o n ( 5 ) o f t h e t h e s i s i s now a v a i l a b l e .
WC
CWA
WR
RWA
RS
= 4.7062
=
. 7416
= 3. 8941
=
. 8 3 65
=
. 8282
Based on t h e abov e d a t a , AE = 22.5%
absolute
e x tra c tio n
as
per
65
APPENDIX C
RESULTS OF EXTRACTION RUNS
66
Table
Run
No.
12
11.
Absolute E x tra c tio n
E x p e r i m e n t Run.
Absolute
E xtra ctio n
(%)
Solvent
R etention
(g/g res)
V a l u e s and S o l v e n t
I:
Il
I!
R etention
for
Each
Absolute
Solvent
Run
E xtra ctio n
R etention
No^_________ (%)__________ ( 9 / 9 r e s )
35.87
0.0412
13
22.50
0.1718
16.05
0. 0 68 1
14
18.46
0.2237
29.62
0. 0201
15
1 9- 46
0.0758
12.81
0.0712
16
16.78
0.1159
35.57*
0.2893
17
16.50
0 .0702
12.92
0.0 816
18
11.04
0.0696
13.00
0. 0201
19
19.78
0.0435
9-99
0.0 679
20
12.74
0.0742
1 9- 66
0.0862
21
21.85
0.2142
34.84
0.2 028
67
APPENDIX D
ERROR ANALYSIS
68
ERROR ANALYSIS
T h i s e r r o r a n a l y s i s uses t h e p r o c e d u r e p r e s e n t e d by H. M i c k l e y
t h e A p p l i e d M a t h e m a t i c s i n C hem ic al E n g i n e e r i n g t e x t b o o k .
(31)
in
The e q u a t i o n used
th is th e sis is:
used
in
to
c o m p ut e
the
a b solute
e x tra c tio n
of
coal
AE = WCj-CWA - WR-RWA--RS
WC5-CWA
where:
WC
CWA
WR
RWA
RS
=
=
=
=
=
w e ig h t o f the coal
c o r r e c t i o n f a c t o r f o r w a t e r and ash i n
w eight o f the re sid u e
c o r r e c t i o n f a c t o r f o r w a t e r and ash i n
c o rre c tio n fa c to r f o r solvent reta in e d
r e s i due
The c o r r e c t i o n f a c t o r f o r
the f o llo w in g e q u a tio n :
water
and
ash
in
the
coal ,
CWA,
th e coal
the residue
in th e
is
given
by
CWA = I - M W - MA
where:
MW = mass f r a c t i o n
MA = mass f r a c t i o n
The c o r r e c t i o n
the f o llo w in g
RWA = I
fa ctor
w a te r in th e coal
ash i n t h e c o a l
f o r w a t e r and as h
in
the
residue,
RWA,
is given
by
e q u a tio n :
- MWR - MAR
where:
MWR = mass f r a c t i o n
MAR = mass f r a c t i o n
Id e n tific a tio n
of
R e la tive
Error o f
w a te r in th e r e s i d u e
a sh i n t h e r e s i d u e
Experim ental
V ariables
B ecause t h e r e s u l t s o b t a i n e d f r o m r u n 17 a p p e a r t o be a v e r a g e , t h e e r r o r
a n a l y s i s c a l c u l a t i o n w i l l be based upon t h a t r u n .
The f o l l o w i n g e x p e r i ­
mental d a ta were o b t a i n e d :
69
O rig in a l
C o ls trip
E xtra ctio n
Coal:
w e i g h t = 5-3344 g
mass f r a c t i o n w a t e r = 0 . 1 78
mass f r a c t i o n ash = 0 . 0 8 0 4
Residue:
w eight = 4.0886 g
mass f r a c t i o n w a t e r = 0 .0 272
mass f r a c t i o n ash = 0. 1 06 1
solvent re te n tio n fa c to r
(as c a l c u l a t e d
u s i n g p r o c e d u r e f o u n d i n A p p e n d i x B) =
0.9 298
The w e i g h t o f t h e c o a l
i n t r o d u c e d t o t h e r e a c t o r was measur ed on a
M e t t l e r H80 a n a l y t i c a l b a l a n c e w i t h s e n s i t i v i t y a t t h e 0 . 1 mg l e v e l .
A s s um in g t h a t no c o a l was l o s t upon i n t r o d u c t i o n t o t h e r e a c t o r , t h e
a u t h o r f e e l s c o n f i d e n t t h a t th e t r u e w e i g h t o f th e coal sample i s w i t h i n
5 mg o f t h e m eas ur ed v a l u e .
The r e l a t i v e
error
re la tiv e
th e re fo re
e r r o r WC
=
is:
*
5.3344
100 = ±0.09%
The w e i g h t o f t h e r e s i d u e was measur ed u s i n g t h e same a n a l y t i c a l b a l a n c e
as used t o me as ur e t h e c o a l s a m p l e s .
A lth o u g h the w e ig h t o f the re s id u e
recovered
is
l i k e l y a c c u r a t e t o ±0.1%,
mass l o s s
in
filte rin g
and
h a n d lin g is suspected.
The a u t h o r f e e l s c o n f i d e n t t h a t no more t h a n 2%
was l o s t and t h e r e f o r e s e t s t h e c o n f i d e n c e l i m i t a t ±2%.
re la tiv e
e r r o r WR = ±2.0%
S e v e r a l w a t e r a n a l y s e s w e r e p e r f o r m e d on t h e c o a l s a m p l e and t h e a u t h o r
has d e t e r m i n e d t h a t a l l meas ur ed w a t e r c o n t e n t v a l u e s l i e w i t h i n ±1.4%
o f the average v a lu e .
Several
ash a n a l y s e s w e r e a l s o p e r f o r m e d on t h e c o a l s a m p l e and t h e
a u t h o r has d e t e r m i n e d t h a t a l l m eas ur ed ash c o n t e n t v a l u e s l i e w i t h i n
±1.0% o f t h e a v e r a g e v a l u e .
Using th e a c c u r a c y l i m i t s s p e c i f i e d above,
w a t e r and as h c o r r e c t i o n f a c t o r f o r t h e c o a l
r.e .
((!-.1780-.080 4)
CWA
-
the
is:
re la tiv e
error
( 1 - . 1780*1.014-.0804*1.01))
*
of
the
]00
( 1 - . 1780-.0804)
=
±0.5%
A l t h o u g h o n l y one ash and w a t e r d e t e r m i n a t i o n was p e r f o r m e d f o r eac h
c o a l - r e s i d u e , i t was assumed t h a t t h e c o n f i d e n c e l i m i t s o f eac h m e a s u r e ­
ment w o u l d be t h e same as f o r t h e c o a l .
The r e l a t i v e e r r o r o f t h e c o a l
r e s i d u e w a t e r and ash c o r r e c t i o n f a c t o r i s :
70
((l-.0 2 7 2 -.1 0 6 l)
r 'e'
RWA
-
( 1 - . 0272*1.014-.1061*1.01))
*
]00
( I - . 0 2 7 2 - . 1061)
=
± 0 . 2%
The f a c t o r used t o c o r r e c t f o r s o l v e n t r e t a i n e d i n t h e c o a l r e s i d u e i s
based upon s e v e r a l a s s u m p t i o n s f o r w h i c h no v e r i f i a b l e p r o o f e x i s t s .
A
c o n f i d e n c e l i m i t was e s t i m a t e d u s i n g l o g i c a l c o n t r a i n t s f o r t h e s y s t e m .
I f no s o l v e n t w e r e r e t a i n e d , t h e n t h e c o r r e c t i o n f a c t o r w o u l d be 1 . 0 .
I f s o l v e n t w e r e r e t a i n e d as w h o l e m o l e c u l e s , t h e n t h e c a l c u l a t e d s o l v e n t
co rre ctio n
f a c t o r s h o u l d be v e r y a c c u r a t e .
F o r run 17» t h e s o l v e n t
c o r r e c t i o n f a c t o r was c a l c u l a t e d t o be 0 . 9 2 9 8 .
I t s h o u l d be r e a s o n a b l y
c e r t a i n t h a t t h e s o l v e n t c o r r e c t i o n f a c t o r f o r r un 17 w i l l be l o c a t e d
bet ween 1 . 0 and 0 . 9 2 9 8 .
I f i t i s assumed t h a t t h e s o l v e n t c o r r e c t i o n
f a c t o r i s a c c u r a t e t o 25% o v e r t h e r a n g e i n w h i c h i t m us t l o g i c a l l y be
l i m i t e d , t h e n i t can be c a l c u l a t e d as f o l l o w s :
re la tiv e
error
RS = ( I - . 9 2 9 8 )
Approximate values o f
*
.25 *
100 = ±1.9%
t h e d a t a and t h e e s t i m a t e d maximum e r r o r s
a re then
the f o l lo w in g :
Approxim ate
Va I ue
Measured
To
WC
5.3344
±0.005 g
WR
4.0 886
±0.082 g
RWA
0.8667
±0.002
CWA
0.7416
±0.004
RS
0.9 298
±0.018
V aria b le
The a b s o l u t e
•each v a r i a b l e
values
of
the
p a rtia l
are:
9AE
9WR
RWA*RS
WC*CWA
0.2037
9AE
9 RWA
WR*RS
WC* CWA
0.9 610
9AE
0.8958
9 RS
WR*RWA
WC* CWA
9AE
9CWA
WR*RWA*RS
WC*CWA2
=
1.1
d e riv a tiv e s
for
AE w i t h
respect
to
71
The maximum d e v i a t i o n
tion
from t he c a l c u l a t e d v a l u e f o r
the a b s o lu te e x t ra c
is t h e n :
SAE
=
100 *
=
±3 -9%
Therefore,
3.9% above
the e r r o r
works o u t
The a u t h o r
(.2037*.082+.9610*.002+.8958*.018+1.123*.004)
t h e e r r o r bar f o r t h e e x t r a c t i o n f o r run 17 should e x t en d
and below t h e c a l c u l a t e d v a l u e .
A lt ho ug h i t is o bvi ous t h a t
b ar i s a f u n c t i o n o f each o f t h e e x p e r i m e n t a l v a r i a b l e s ,
it
t h a t t h e y a r e o f a p p r o x i m a t e l y t h e same l e n g t h f o r each r u n.
has chosen t o use e r r o r bar s o f b% on a l l g r a p h s .
APPENDIX E
"WATER" LOSS JUSTIFICATION
73
"WATER" LOSS JUSTIFICATION
The e l e m e n t a l
C
loss
i n gm o l e s p e r
0.095
H
IOOg w e t c o a l
0.720
0
0.9 97
W i l l any c o m b i n a t i o n o f compounds s u s p e c t e d
t h e c o a l a c c o u n t f o r t h e o b s e r v e d mass l o s s ?
If
it
is
Let:
Elemental
It
assumed t h a t
being
v o la tiliz e d
from
then:
W = moles o f w a te r
C = moles o f carbon d i o x i d e
M = m o l e s o f met hane
Balance E q u a tio n s :
C + M = 0.095
2W + 4M = 0 . 7 2 0
W + 2C = 0 . 9 9 7
Simultaneous
so lu tio n
i s assumed t h a t
Elemental
of
H2 O, CO2 , and CH^ a r e v o l a t i l i z e d ,
C balance:
H balance:
0 balance:
Let:
is:
y ie ld s :
im possible s o lu tio n
f o r methane.
H2 O, CO2 , and O2 a r e v o l a t i l i z e d ,
W = moles o f w a te r
C = moles o f carbon
0 = m o l e s o f o xy gen
d io xid e
Balance E q u a tio n s :
. C balance:
H balance:
0 balance:
C = 0.0 95
2W = 0 . 7 2 0
W + 2C + 20 = 0 . 9 9 7
Sim ultaneous s o l u t i o n
y ie ld s :
C = 0.095
T h is appears t o
be a p l a u s i b l e
W = 0.36
s o lu tio n .
0 = 0.22
n e g a tiv e value
then:
MONTANA STATE UNIVERSITY LIBRARIES
stks N378.L897
Extraction of Colstrip coal using supers
3 1762 00190254 I
Main
N3T8
I 1Q g tJ
cop.2
DATE
,
Losinski, Sylvester J.
Extraction of C o l s t n p
coal using supersolvents
IS S U E D TO
Main
N378
L89T
cop. 2