Continuous short residence time coal liquefaction using metal chloride-hydrogen chloride catalysts
by John Jay Waterman
A thesis submitted in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE
in Chemical Engineering
Montana State University
© Copyright by John Jay Waterman (1979)
Abstract:
A continuous short residence time coal liquefaction process was analyzed for its capability to
catalytically hydrogenate pulverized coal, using a metal chloride, hydrogen-chloride catalyst system.
The coal studied was Rosebud sub-bituminous coal from Colstrip, Montana. The process consisted of a
continuous coal feeder which delivered coal to an Inconel, tubular reactor which was run between 400
and 600°C and 500 and 1,000 psig. The coal was carried through the reactor entrained in a flow of
hydrogen or a mix of hydrogen and hydrogen chloride. Six different metal chloride catalysts were
impregnated on coal and tested for conversion. Analysis included coal conversion by hexane, toluene,
and pyridine soluble fraction and nitro gen and sulfur determination.
Results indicated that the addition of metal chlorides to coal significantly increased the level of coal
conversion over non-catalytic coal. The presence of hydrogen chloride in the feed gas greatly increased
coal conversion in both catalytic and non-catalytic coals.
The effect of three operating variables on nickel chloride impregnated catalytic coal was also
determined. The coal conversion was shown to increase with increasing temperature and pressure, and
to decrease with increasing carrier gas flow rate. S T A T E M E N T OF PERMISSION TO COPY
In p re s e n tin g t h is th e s is in p a r tia l fu lf illm e n t o f th e re q u ire m e n ts
f o r an a d va n ce d d e g re e a t M ontana S ta te U n iv e r s it y ,
I a g re e th a t th e
L ib r a r y sh a ll make i t f r e e ly a v a ila b le f o r in s p e c tio n .
I f u r t h e r agree
t h a t p e rm is s io n f o r e x te n s iv e c o p y in g o f th is th e s is f o r s c h o la rly p u r ­
poses m ay be g ra n te d b y my m ajor p r o fe s s o r , o r , in h is absence b y
th e D ire c to r o f L ib r a r ie s .
I t is u n d e rs to o d t h a t a n y c o p y in g o r p u b li­
c a tio n o f t h is th e s is f o r fin a n c ia l g a in s h a ll n o t be allow ed w ith o u t my
w r itte n p e rm is s io n .
S ig n a tu re
Date
/(& /< ? 7 4
C O N T IN U O U S SH O R T RESIDENCE T IM E CO AL L IQ U E F A C T IO N USING
M E TA L C H LO R ID E -H Y D R O G E N C H LO R ID E C A T A L Y S T S
by
JOHN JA Y WATERMAN
A th e s is s u b m itte d in p a r tia l fu lf illm e n t
o f th e re q u ire m e n ts f o r th e d e g re e
of
MASTER OF SCIENCE
in
Chem ical E n g in e e rin g
A p p ro v e d :
C h a irp e rs o n , G ra d u a te Com m ittee
H ead, M ajor D e par
G ra d u a te Drean
M O N TAN A S T A T E U N IV E R S IT Y
Bozem an, M ontana
M a rc h , 1979
iii
ACKNOW LEDGMENT
T h e a u th o r w ish e s to th a n k th e s t a f f o f th e Chem ical E n g in e e rin g
D e p a rtm e n t a t M ontana S ta te U n iv e r s ity f o r t h e ir s u g g e s tio n s w h ich led
to th e co m p le tio n o f th is r e p o r t.
S pecial th a n k s go to D r .
F. P.
M cC and Ie ss, d ir e c to r o f th is re s e a rc h , f o r h is a ssista n ce and g u id a n c e
t h r o u g h o u t th is in v e s tig a tio n .
T h a n k s a re e xte n d e d to M r. James
T i lle r y , th e la te M r. S ila s . H u so, and M r.
Lym an .Fellows f o r t h e ir h e lp
in m a in ta in in g th e re s e a rc h a p p a ra tu s .
T h e a u th o r w ish e s to th a n k th e N a tio n a l S cience F o u n d a tio n f o r
t h e ir fin a n c ia l s u p p o r t.
T h e w o rk was done u n d e r NSF G ra n t No. E n g .
74-23009.
S pecial th a n k s go to Ron N o v ic h , B ill Sam pson, and S a n d y H inds
f o r t h e ir h e lp w ith a n a ly tic a l w o rk .
F in a lly and m ost s in c e re ly , th e a u th o r w ishes to th a n k h is w ife ,
S ta c ie , f o r h e r c o n s ta n t e n c o u ra g e m e n t and s u p p o r t t h r o u g h o u t th e
p r o je c t and f o r th e tim e s p e n t in p r e p a rin g th is m a n u s c rip t.
,
T A B L E OF C O N TEN TS
Page
V IT A
........................................................................................................
ACKNOW LEDG M ENT
T A B L E OF C O N TEN TS
ii
. ................................................ ..............................
ill
...............................................................................
iv
L IS T OF T A B L E S
..........................
vi
■LIST OF FIGURES
........................................................................................
v ii
A B S T R A C T ..................................
IN T R O D U C T IO N
............................................
B.
C.
D.
E.
F.
G.
H.
I.
.
U n iv e r s ity o f U ta h 's C o n tin u o u s Coal
H y d ro g e n a tio n Process
....................................................
C itie s S e rv ic e R esearch and D evelopm ent
S h o rt R esidence Tim e Coal H y d ro p y ro ly s is . . . .
S p e n c e r Chem ical C om pany P r o c e s s ...................................
B ro o k h a v e n N a tio n a l L a b o ra to ry FHP Process . . . .
I n s titu te o f Gas T e c h n o lo g y R is e r C ra c k in g
o f Coal P r o c e s s ..........................................................................
R ockw ell In te rn a tio n a l P a rtia l L iq u e fa c tio n
FHP P r o c e s s .......................................
O c c id e n ta l R esearch C o rp o ra tio n Flash
P y ro ly s is Process S y s t e m ....................................................
O th e r R e s u l t s ........................................................
M ontana S ta te U n iv e r s ity R e s e a r c h ...................................
RESEARCH O B J E C T IV E S ..........................................................................
I
^ r-
C u r r e n t D om estic E n e rg y S i t u a t i o n ...................................
T h e S t r u c tu r e o f C o a l ...............................
Coal L iq u e fa c tio n ,............................................
P ro d u c ts o f Coal L iq u e fa c tio n Processes
Coal L iq u e fa c tio n P r o c e s s e s ....................................................
S h o rt R esidence Tim e Coal L iq u e f a c t io n ..........................
R E LA TE D R E S E A R C H .......................... ....................................................
A.
I
cm
A.
B.
C.
D.
E.
F.
v iii
12
15
18
18
19
21
22
23
26
27
28
28
30
V
M A T E R IA L S , EQ U IPM EN T, AN D P R O C E D U R E S ...................... , .
A.
B.
C.
D.
E.
F.
G.
H.
I.
J.
Process D e s c rip tio n ......................................................................
Coal S ta r F e e d e r ..........................................................................
R e a cto r and H e a te r A s s e m b ly ................................................
P ro d u c t C o lle c tio n and S ystem P re s s u re
......................
T e m p e ra tu re M easurem ent and H y d ro g e n Flow
M e a s u r e m e n t ...............................................................................
P re p a ra tio n and A n a ly s is o f C o a l ......................................
P re p a ra tio n o f C a ta ly tic Coal
............................................
P ro c e d u re f o r P e rfo rm in g a T e s t R u n ..............................
D e te rm in a tio n o f C o n v e r s io n ................................................ .
S u lf u r and N itro g e n D e te rm in a tio n
...................................
RESU LTS AN D D ISC USSIO N
A.
B.
C.
D.
E.
F.
G.
H.
I.
31
31
31
35
35
37
38
42
43
45
49
..................................................................
50
Coal A n a ly s is
.................................................................
C old Flow F e e d ra te T e s t s ........................................................
P re lim in a ry R e s e a r c h .........................
T h e E ffe c t o f C a ta ly s is on Coal C o n v e r s io n ..................
T h e E ffe c t o f H y d ro g e n C h lo rid e on Coal
C o n v e r s io n ...................................................................................
T h e E ffe c t o f T e m p e ra tu re oh Coal
C o n v e r s io n ...................................................................................
T h e E ffe c t o f C a r r ie r Gas F lo w ra te on
Coal C o n v e r s i o n .........................................................' . . .
T h e E ffe c t o f P re s s u re on Coal C o n v e r s io n .................
S u lf u r and N itro g e n C o n te n t o f O il and
A s p h a lte n e F r a c t io n s .............................................................
50
52
55
57
60
63
65
67
69
C O N C L U S IO N S ................................................................................................
71
RECO M M ENDATIO NS FOR FUTUR E S T U D Y
73
...................................
A P P E N D I X .................................................................................................................... 77
L IT E R A T U R E C IT E D
82
vi
L IS T OF T A B LE S
T a b le
Page
I.
C itie s S e vice Process Run C o n d i t i o n ................................
20
II.
A n a ly s is o f C o ls trip S u b -B itu m in o u s C o a l .......................
39
III.
C old Flow T e s tin g O p e ra tin g P a r a m e t e r s ......................
53
IV .
Some P re lim in a ry R e s u lt s .........................................................
56
V.
F u r th e r R e s u lts o f P re lim in a ry R e s e a r c h .......................
56
V I.
S ta n d a rd Run C o n d it io n s .........................................................
57
V l I.
M etal C h lo rid e . C a ta ly s ts and Coal C o n c e n tra tio n s . .
58
V III.
T h e E ffe c t o f M etal C h lo rid e C a ta ly s ts on
Coal C o n v e r s i o n ......................................................................
59
T h e E ffe c t o f Metal C h lo rid e C a ta ly s ts on
In d iv id u a l Coal C o n v e r s io n ................................................
59
T h e E ffe c t o f H y d ro g e n C h lo rid e on Coal
C o n v e r s io n ...................................................................................
62
T h e E ffe c t o f H y d ro g e n C h lo rid e on In d iv id u a l
Coal C o n v e r s i o n ..................................................................
62
N itro g e n and S u lfu r in HCI R u n s ........................................
63
X III.
R e a cto r Gas R esidence T i m e s ..................................
67
X IV .
O il and A s p h a lte n e S u lf u r and N itro g e n C o n te n t
IX .
X.
X I.
X II.
. .
70
XV.
T y p ic a l Run D a t a .......................................................................
78
X V I.
R e su lts o f P re lim in a ry R e s e a r c h .......................................
79
X V II.
Final Run D a ta , O p e ra tin g P a r a m e t e r s ..........................
80
X V III.
Final Run D a ta , C o n v e r s i o n ................................................
81
v ii
L IS T OF FIGURES
F ig u re
1.
2.
3.
4.
Page
D is tr ib u tio n o f D om estic D e m o n stra te d
Coal R e s e r v e s ..........................................................................
T y p ic a l S t r u c tu r e o f S u b -B itu m in o u s
C o a l ..........................
5
M obil R esearch Coal L iq u e fa c tio n P ro d u c t
C h a ra c te riz a tio n
....................................................
G eneral S t r u c tu r e o f A v e ra g e A s p h a lto l
M o le c u le ..............................................................................
3
10
. .
11
5.
C o n v e rs io n o f Coal v s . Tim e o f R e a c tio n ......................
16
6.
I n s titu te o f Gas T e c h n o lo g y S o lid Feeding
S y s t e m .......................................................................................
25
7.
P rocess Flow D ia g r a m ..................................
32
8.
Coal S ta r F e e d e r ......................................................................
33
9.
T h re e C u b ic C e n tim e te r S ta r S h a f t ...............................■
34
10.
R e a cto r and H e a te r D e t a i l .....................................................
36
11.
A p p a ra tu s Used to D e te rm in e M o is tu re
C o n te n t o f C o a l ......................................................................
41
S o x h le t E x tra c tio n A p p a ra tu s Used to
D e te rm in e Coal C o n v e r s i o n ............................................
47
T h e E ffe c t o f C a r r ie r Gas F lo w ra te on
Coal F e e d r a t e ..........................................................................
54
T h e E ffe c t o f T e m p e ra tu re on Coal
C o n v e r s i o n ...............................................................................
64
T h e E ffe c t o f C a r r ie r Gas F lo w ra te on
Coal C o n v e r s io n ......................................................................
66
T h e E ffe c t o f P re s s u re on Coal C o n v e rs io n
68
12.
13.
14.
15.
16.
viii
ABSTRACT
A c o n tin u o u s s h o r t re s id e n c e tim e coal liq u e fa c tio n p ro ce ss was
a n a lyze d f o r its c a p a b ility to c a ta ly tic a lly h y d ro g e n a te p u lv e riz e d coal,
u s in g a m etal c h lo rid e , h y d r o g e n - c h lo r id e c a ta ly s t s y ste m .
T h e coal s tu d ie d was R osebud s u b -b itu m in o u s coal fro m C o ls t r ip ,
Montana.. .The p ro ce ss c o n s is te d o f a c o n tin u o u s coal fe e d e r w h ich
d e liv e re d coal to an In c o n e l, t u b u la r re a c to r w h ic h was ru n betw een
400 and 600°C and 500 and 1,000 p s ig . T h e coal was c a r rie d th ro u g h
th e re a c to r e n tra in e d in a flo w o f h y d ro g e n o r a m ix o f h y d ro g e n
and h y d ro g e n c h lo rid e .
S ix d if f e r e n t metal c h lo rid e c a ta ly s ts w ere
im p re g n a te d on coal and te s te d f o r co n ve rsio n .. A n a ly s is in c lu d e d coal
c o n v e rs io n b y h e x a n e , to lu e n e , and p y r id in e s o lu b le fr a c tio n and n itr o
gen and s u lf u r d e te rm in a tio n .
R e su lts in d ic a te d t h a t th e a d d itio n o f metal c h lo rid e s to coal
s ig n if ic a n tly in c re a s e d th e level o f coal c o n v e rs io n o v e r n o n -c a ta ly tic
coal. T h e p re se n ce o f h y d ro g e n c h lo rid e in th e feed gas g r e a tly
in c re a s e d coal c o n v e rs io n in b o th c a ta ly tic and n o n -c a ta ly tic coals.
T h e e ffe c t o f th r e e o p e ra tin g v a ria b le s on n ic k e l c h lo rid e im p re g ­
n a te d c a ta ly tic coal was also d e te rm in e d . T h e coal c o n v e rs io n was
show n to in c re a s e w ith in c re a s in g te m p e ra tu re and p r e s s u r e , and to
decrea se w ith in c re a s in g c a r r ie r gas flo w ra te .
IN T R O D U C T IO N AN D BACKG R O U ND
A.
C u r r e n t D om estic E n e rg y C o n d itio n
E n e rg y is th e b a ckb o n e o f o u r m odern te c h n ic a l s o c ie ty .
Its
h e a v y in flu e n c e on n e a rly e v e r y a s p e c t o f o u r e v e ry d a y liv e s has d e ­
v e lo p e d in such a m a n n e r t h a t fe w re a liz e d th e scope o f o u r d e p e n ­
d e n c y u n til th e A ra b O il Em bargo o f 1973.
A s we become e v e r in c re a ­
s in g ly d e p e n d e n t on fo re ig n c ru d e o il, o u r c o u n tr y has la u n ch e d an
in te n s e e f f o r t to f in d a lte r n a tiv e e n e rg y s o u rc e s .
v o ra b le tra d e s itu a tio n s w ith e n e r g y - r ic h
T h e p re s e n t u n fa ­
Ira n and M exico due to p o li­
tic a l u n r e s t, s ta n d to in te n s ify th is p ro b le m .
In a d d itio n , th e U n ite d
S ta te s is also s u ffe r in g fro m decrea sed p ro d u c tio n o f d o m e stic c ru d e
o il.
T h e U n ite d S ta te s s u p p ly o f c ru d e o il has a h u g e im p a c t on th e
w o rld econom ic s itu a tio n as is c u r r e n t ly d e p ic te d b y r is in g in fla tio n ,
n e g a tiv e balance o f tr a d e , and th e w o rld w id e d e v a lu a tio n o f th e U .S .
d o lla r .
I t can be seen th e n , t h a t in o r d e r f o r th e U n ite d S tates to
re ta in its s ta n d a rd o f liv in g and econom ic in d e p e n d e n c e , i t m ust d e fin e
a lte r n a tiv e e n e rg y s o u rc e s .
T h e U n ite d S ta te s has m ore e n e rg y a v a ila b le on a B tu basis in th e
fo rm o f coal th a h in petroleum ,, n a tu ra l g a s , oil sh a le , and t a r sands
com bined [ I ] .
In lig h t o f o u r c u r r e n t e n e rg y s h o rta g e s , th e in cre a se d
2
use o f coal to s a tis fy o u r needs is e s s e n tia l.
H o w e ve r, s o lid fu e l can
o n ly be c u r r e n t ly a p p lie d to a lim ite d p o rtio n o f o u r to ta l e n e rg y
dem and w h ile e n e rg y use in th e t r a n s p o r ta tio n , h o u se h o ld and com m er­
cia l areas a re t o ta lly d e p e n d e n t on liq u id and gaseous fu e ls .
In. a d d i­
t io n , m ost o f th e e n e rg y consum ed in in d u s t r y comes fro m liq u id and
gaseous fu e ls .
T h e re fo r e , i t w o u ld be h ig h ly d e s ira b le to c o n v e rt
coal to com m ercial q u a n titie s o f liq u id fu e l.
A c c o rd in g to f ig u r e s re p o rte d b y th e 1974 W orld E n e rg y C o u n c il,
th e U n ite d S ta te s has a b o u t 25 p e rc e n t o f th e w o rld 's re c o v e ra b le coal
beds [ I ] .
T h is coal a cc o u n ts f o r 9 4 .5 p e rc e n t o f th e U .S . fo s s il
re s e rv e [ 2 ] .
O f th e n e a rly 800 b illio n to n s o f coal re c o v e ra b le fro m
e x is tin g coal re s e rv e s , alm ost t h i r t y p e rc e n t are located in th ic k beds
w h ic h a re m ineable b y e x is tin g s t r ip m in in g te c h n o lo g y [ 3 ] .
F ig u re I
show s t h a t 41 p e rc e n t o f th e d e m o n s tra te d coal re s e rv e base is located
in th e N o rth e rn R o cky M o u n ta in R e g io n .
B.
T h e S tr u c tu r e o f Coal
Coal is a c a rb o n a c e o u s , c o m b u s tib le s o lid w h ich o r ig in a te d fro m
th e a c c u m u la tio n and b u r ia l o f p a r t ia lly decomposed v e g e ta b le m a tte r
fro m p re v io u s g e o lo g ica l ages [ 4 ] .
B io lo g ic a l changes and s u b s e q u e n t
ch a n g e s o f te m p e ra tu re and p re s s u re a lte re d th e se d e p o s its o f coal such
t h a t coal is n o t a u n ifo rm su b s ta n c e and no tw o coals a re th e same in
3
NORTHERN ROCKY MOUNTAINS
(ND. SO. M T. W Y 1 ID)
SOUTHERN APPALACHIAN BASIN
(EASTERN K Y 1 VA1TN1 HC1 GA, AL)
WESTERN INTERIOR BASIN
' (XS. MO. OK, AR. T X )
_
W EST COAST
(A K . W A. OR. CA)
SOUTHERN ROCKY MOUNTAINS
( CO. UT1 AZ, HM )
ILLINOIS BASIN
( II . IN. WESTERN KY)
HOiiriIERN APPALACHIAN BASIN
(PA. CR, W V. MO)
. MICHIGAN BASIN
(NEGLIGIBLE AMOUNT)
Source: U S. Geological Survey Bulletin No. 1412.
F ig u re I .
D is tr ib u tio n o f D om estic D e m o n s tra te d C o al R e se rve s [ I ] .
4
e v e r y re s p e c t.
S ince in c re a s in g g e o lo g ica l age b u rie d coal d e e p e r and
com pressed i t m o re , th e d e p th a t w h ic h coal is fo u n d g iv e s a ge n e ra l
g u id e as to its r a n k .
H ig h r a n k coals b u rie d deep and m ined u n d e r ­
g ro u n d a re a n th r a c ite and b itu m in o u s , w h ile s h a llo w e r, s t r ip m ineable
coals a re lo w e r ra n k s o f s u b -b itu m in o u s and lig n ite .
T h e d iff e r e n t
ra n k s ha ve a w id e ra n g e o f co m p o sitio n as w ell as chem ical and p h y s i­
cal p r o p e r tie s .
Coal is p r im a r ily com posed o f c a rb o n , h y d r o g e n , . and
o x y g e n w ith m in o r am ounts o f s u lf u r and n itro g e n as w ell as v a r y in g
am ounts o f m o is tu re and m in e ra ls .
From chem ical c h a ra c te riz a tio n w o rk p e rfo rm e d on b itu m in o u s c o a ls,
i t a p p e a rs t h a t long c h a in , sim ple a lip h a tic and a lic y c lic h y d ro c a rb o n
g ro u p s re p re s e n t th e b u lk o f th e coal m olecu le.
r in g s tr u c tu r e s a re a p p a r e n tly a b s e n t.
M u ltip le p o ly n u c le a r
A lth o u g h coals w e re once
th o u g h t to have 50 o r 60 o f th e r in g s t r u c tu r e s connected., i t a pp ears
t h a t o n ly f iv e o r s ix a c tu a lly com bin e.
A model o f th e s tr u c t u r e is
show n in F ig u re .2 [ 5 ] .
C.
Coal L iq u e fa c tio n
Coal liq u e fa c tio n b y h y d ro g e n a tio n u n d e r p re s s u re a t elevated
te m p e ra tu re s was f i r s t s tu d ie d b y B e rg iu s in 1913.
B y th e 1940's,
G erm any had n in e com m ercial p la n ts p ro d u c in g liq u id fu e ls fro m c o a l.
T h e te c h n o lo g y ceased to be d e ve lo p e d f u r t h e r due to th e th e n low
co sts o f n a tu ra l gas and c ru d e o il.
5
S
Il-C -H
O
H-C-K
t - C *-C
V
OH
C= O
HO
H2-9H
A.
C-OH
OH
OH
OH
A3
O
C -O - O
K O -C -,
H
H
C-C-O
H
-C— C —
H
H H
a %
H
-R 3 —c
tU
K
v —rfs"-cH
C=O
R0N A lic y c lic R in g s o f N C a rb o n s
RN
A lk y l S id e C h a in s o f N C a rb o n s
R1N
U n s a tu ra te d A lk y l C h a in s
CB
C ro s s -b o n d in g to O th e r H e te ro c y c lic G ro u p s
T
T e tr a h e d r a l B onds
F ig u re 2.
T y p ic a l S t r u c tu r e o f S u b -B itu m in o u s Coal [ 7 ] .
H
6
T e c h n iq u e s f o r c o n v e rtin g coal to liq u id fu e ls a re now b e in g
im p ro v e d w ith th e c u r r e n t em phasis b e in g placed on th e d e ve lo p m e n t
o f fu e ls s u ita b le f o r b o ile r fe e d s and r e fin e r y fe e d s to c k s .
Coal has a c a rb o n to h y d ro g e n w e ig h t ra tio ( C / H ) ra n g in g fro m
12 f o r lig n ite coals to above 20 f o r a n th r a c ite coal.
T o c o n v e rt coal
to liq u id s , i t is n e c e s s a ry to in c re a s e th e h y d ro g e n c o n te n t o f th e
c o a l.
T h is h y d ro g e n a tio n p ro ce ss is th e r e s u lt o f a d d in g a h y d ro g e n
m olecule to an u n s a tu ra te d c a rb o n -c a rb o n b o n d .
I f th e C /H ra tio is
lo w ered to 10, a t h ic k , , v is c o u s s y n th e tic c ru d e o il is p ro d u c e d .
By
in c re a s in g th e d e g re e o f h y d ro g e n a tio n to a C /H r a tio o f 3, m ethane
gas can be fo rm e d .
In th e coal liq u e fa c tio n p ro c e s s , i t is b e lie v e d t h a t th e h y d r o ­
g e n a tio n p ro ce ss is accom panied b y th e d eco m p osition o f la rg e m olecu­
la r w e ig h t com pounds in to sm a lle r fra g m e n ts [ 6 ] .
I f th e coal is heated
in a norm al p y r o ly s is p ro c e s s , th e rm a l c ra c k in g and p o ly m e riz a tio n
o c c u r w ith p ro d u c ts su ch as p a r a ffin s , o le fin s , a ro m a tic s , t a r , co ke ,
c h a r , and p o ly c o n d e n s e d p itc h b e in g fo rm e d .
I f th e coal is heated in
p re se n ce o f a c a ta ly s t, th e am ount o f p o ly m e riz a tio n is c o n tro lle d and
m ore u s e fu l p ro d u c ts a re fo rm e d , th o s e b e in g In g e n e ra l a lk y la te d a ro ­
m a tic s , liq u id s and h y d ro c a rb o n gases.
I t has been re p o rte d t h a t as th e C /H ra tio o f th e coals in c re a s e ,
th e c o n v e rs io n o f coal to liq u id p ro d u c ts d e cre a se , th e ideal in itia l
7
r a tio b e in g 16 [ 7 ] .
T h e C o ls tr ip , M o n tana, s u b -b itu m in o u s coal used
in t h is th e s is w o rk has a C /H r a tio o f 1 4 .5 .
D.
P ro d u c ts o f Coal L iq u e fa c tio n
A common means o f fra c tio n a tio n and c h a ra c te riz a tio n o f coal liq u e fa c ­
tio n p ro d u c ts is th r o u g h a s e rie s o f s o lv e n t e x tra c tio n s .
T h e m ajor
c la s s ific a tio n s o f fr a c tio n s a re :
(1 )
O ils -
hexa ne s o lu b le fr a c tio n .
(2 )
A s p h a lte n e s -
hexa ne in s o lu b le , benzene o r to lu e n e so lu b le
f r a c t io n .
(3 )
A s p h a lto ls -
benzene o r to lu e n e in s o lu b le , p y r id in e so lu b le
f r a c t io n .
O f th e s e , th e a sp h a lte n e and a s p h a lto l a re th o u g h t to be re s p o n ­
s ib le f o r h ig h v is c o s ity and p ro c e s s in g d iff ic u ltie s in th e v a rio u s coal
liq u e fa c tio n p ro cesse s [ 9 ] .
T h e o il p r o d u c t is th e m ost d e s ira b le sin ce i t may be used
d ir e c t ly as a fe e d s to c k in e x is tin g r e f in e r y te c h n o lo g y .
T h e o ils have
th e h ig h e s t d e g re e o f h y d ro g e n a tio n o f th e th re e liq u id p ro d u c ts .
A s p h a lte n e s a re c o n s id e re d to be one o f th e p r in c ip a l in te rm e d i­
ates in th e c o n v e rs io n o f coal to an o il p r o d u c t.
I t has been s u g g e s te d t h a t a sp h a lte n e s are th e coal "m o n o m e r",
t h a t is th e sm a lle st u n it o f coal t h a t s t ill re ta in s th e s p e c tra l q u a litie s o f
th e w h ole c o a l.
A d d itio n a l h y d ro g e n a tio n o f a sp h a lte n e s to o ils is a v e r y
8
d i f f ic u l t s te p .
In W e lle r's m echanism o f coal liq u e fa c tio n b y th e f i r s t
o r d e r s e rie s re a c tio n o f coal to a s p h a lte n e fo llo w e d b y a s p h a lte n e to oil
he re p o rte d th e ra te c o n s ta n t a t 400°C o f th e f i r s t re a c tio n to be
t w e n t y - f iv e tim es g r e a te r th a n th e second o r o il p ro d u c in g re a c tio n
[1 0 ].
A s p h a lte n e s ha ve been show n to ha ve h y d ro g e n bon ded a c id -
base com plexes w ith s e p a ra te species h a v in g o n ly an acid o r a base
c h a ra c te r [1 1 ].
I t has been c o n c lu d e d th a t m ost o f th e o x y g e n in
a sp h a lte n e s a re tie d u p in p h e n o lic h y d r o x y l g ro u p s and a b o u t o ne f o u r th o f th e a c tiv e h y d ro g e n is associated w ith n itro g e n h e te ro a to m s.
T h e re is s t ill a q u e s tio n as to th e e x a c t chem ical f u n c t io n a lity o f
a sp h a lte n e s [1 2 ].
A s p h a lto ls a p p e a r to be v e r y h ig h ly fu n c tio n a l p o ly p h e n o ls w ith
m ore th a n te n p e rc e n t h e te ro a to m s .
T h e y have a g r e a te r b a s ic ity and
h ig h e r o x y g e n c o n te n t th a n a s p h a lte n e s .
T h e y have also been shown
to c r o s s - lin k and p o ly m e riz e v e r y r e a d ily [1 1 ].
I t has been shown
t h a t f o r low c o n v e rs io n o f co a l, th e a s p h a lto l p r o d u c t re p re s e n ts u p to
80 p e rc e n t o f th e to ta l p r o d u c t [9 , 1 3 ].
T h e te rm a s p h a lto l was o r i ­
g in a lly p ro p o se d d u e to th e e v id e n c e sh o w in g th a t a s p h a lto ls could be
d is tin g u is h e d fro m a sp h a lte n e s b y a h ig h e r d e g re e o f fu n c t io n a lity
in th e fo rm o f m ore h y d r o x y g ro u p s p e r m olecule [9 , 1 3 ].
In o r d e r to f in d a m ore fu n d a m e n ta l u n d e rs ta n d in g o f th e chem i­
cal n a tu re o f coal liq u e fa c tio n p r o d u c ts , M obil R esearch and D e ve lo p ­
m ent C o rp o ra tio n d e ve lo p e d a m ethod o f chem ical fra c tio n a tio n
[1 3 ].
9
T h e ir b asis was t h a t e x tra c tio n to ld lit t le a b o u t th e liq u e fa c tio n p r o ­
d u c ts fro m a chem ical s ta n d p o in t s in c e s o lu b ilit y d e p e n d s n o t o n ly on
m o le cu la r w e ig h t, c a rb o n s k e le to n , and chem ical f u n c t io n a lit y , b u t also
in te ra c tio n s w ith o th e r s o lu b le species w h ic h can also a c t as s o lv e n ts .
T h e y p o s tu la te d t h a t d e p e n d in g on th e p re se n ce o r absence o f o th e r
species in coal liq u id , a m olecule co u ld end up as e ith e r an oil o r
a s p h a lte n e .
T h e m ethod d e ve lo p e d was a liq u id c h ro m a to g ra p h ic p r o ­
c e d u re u s in g s ilic a gel as th e s ta tio n a r y phase [1 4 ].
T h e e lu tio n s o l­
v e n ts , a p p a re n t chem ical cla sse s, and e x tra c tio n c la s s ific a tio n is
show n in F ig u re 3.
I t is show n t h a t o ils c o n ta in some n o n - h y d r o c a r ­
bon com pounds w h ic h a re p r im a r ily e th e r s , and t h a t a sp h a lte n e s are
f o r th e m ost p a r t m o n o fu n c tio n a l.
M obile also re p o rte d t h a t th e w e ig h t
p e rc e n t o f he te ro a td m s in th e oil fr a c tio n is a b o u t I p e rc e n t o r less
w h ile a b o u t 2 p e rc e n t in a sp h a lte n e s and 10 p e rc e n t in a s p h a lto ls .
As
a r e s u lt o f th e M obil w o r k , a model was deve lo p e d f o r th e a ve ra g e
chem ical s t r u c t u r e o f an a s p h a lto l m olecule g e n e ra te d fro m West K e n­
t u c k y coal ( F ig u r e 4 ) , th e s t r u c t u r e f o r th e a ve ra g e com pound com ing
fro m th e s o lu tio n e lu te d in t e t r a h y d r o f u r a n .
M O B IL F R A C T IO N A T IO N . PROCEDURE
C lassical D e s c rip tio n
F ra c tio n
E lu tio n S o lv e n t
M ajor C om pounds
O ils ( 1 - 3 )
I
2
3
Hexane.
Hexane/15% Benzene
C h lo ro fo rm
S a tu ra te s
A ro m a tics
P olar a ro m a tic s ; n o n basic N , 0 , S -h e te ro c y c lic s
A s p h a lte n e s ( 3 - 5 )
4'
Sim ple phe n o ls
5
C h loroform /10%
E t9O
EtgO/3% EtOH
6
MeOH
7
8
C H C L/3% EtOH
THF ^
A s p h a lto ls (5 t h r u 9 )
9
10
F ig u re 3.
M obil F ra c tio n a tio n P ro c e d u re .
Basic n itro g e n h e te ro c y c lic s , d i and
trip h e n o ls
H ig h ly -fu n c tio n a l
m olecules ( g r e a te r
th a n 10% h e te ro a to m s)
P olyph enols
In c re a s in g O c o n te n t
and n itro g e n b a s ic ity
P y r id in e
N o n -e lu te d , u n k n o w n
m ate rials
11
F ig u re 4
^6 1 ^4 6 ^2 ^4
73% A r o m a t ic Carbon
900 Mo l , W i,
60% A r o m a t ic Hydrogen
G eneral S t r u c tu r e o f A v e ra g e A s p h a lto l M olecu le [1 3 ].
12
E.
Coal L iq u e fa c tio n Processes
T h e p ro d u c tio n o f liq u id s fro m coal can be done b y f o u r g e n e ra l
m e th o d s:
(1 )
H y d ro liq u e fa c tio n .
(2 )
S o lv e n t e x t r a c tio n .
(3 )
P y r o ly s is .
(4 )
L iq u id h y d ro c a rb o n c a ta ly tic s y n th e s is .
H y d ro liq u e fa c tio n is th e d ir e c t c a ta ly tic h y d ro g e n a tio n o f coal
u n d e r e le v a te d p re s s u re and te m p e ra tu re .
In th e g e n e ra l p ro c e s s , coal
is s lu r r ie d w ith a coal d e riv e d re c y c le o il and th e n m ixed w ith gaseous
h y d ro g e n and fe d in to a re a c to r r u n a t a b o u t 8 5 0 °F and fro m 2,000 to
4,000 p s ig .
One o f th e b e s t c a ta ly s ts a p p e a rs to be c o b a lt m o ly b d a te .
T h e m ain p r o d u c t o f t h is p ro ce ss is a h e a v y o i l, and th e coal h e te ro ­
atoms ( s u lf u r , o x y g e n , and n itr o g e n ) leave as low m o le c u la r w e ig h t
gase s.
A n exam ple o f h y d r o liq u e fa c tio n in c lu d e s th e f i r s t com m ercial
p ro ce ss f o r c o n v e rtin g coal to liq u id s .
T h e B e rg iu s p ro ce ss g e n e ra ­
te d g a s o lin e and m id d le o ils f o r G erm any d u r in g W orld W ar Il a t a peak
p ro d u c tio n o f 64,200 b a r r e ls p e r d a y .
T h is p ro ce ss o p e ra te d a t 800°F
to 900°F and 250 to 700 a tm o spheres u s in g an iro n s u lfa te -s o d iu m s u l­
fid e c a ta ly s t.
T h e S y n th o il pro ce ss d e ve lo p e d b y th e U .S . B u re a u o f
M ines is also a h y d r o liq u e fa c tio n p ro c e s s .
In th is m e th o d , a s y n th e tic
c ru d e o il w ith a h e a tin g v a lu e o f 17,000 B t u / lb is g e n e ra te d a t a y ie ld
o f 3 .3 b a r r e ls p e r to n o f coal.
I
T h e s u lf u r c o n te n t is s t ill f a ir ly h ig h .
13
alm ost 0 .3 w e ig h t p e rc e n t in th e p r o d u c t.
C o b a lt m o ly b d a te c a ta ly s t
im p re g n a te d on a s ilic a pro m o te d alum ina s u p p o r t is used to c a ta lyze
th e re a c tio n a t SSO0F a n d 4000 p s ig .
O th e r exam ples o f h y d r o liq u e fa c ­
tio n in c lu d e th e C o-S team p ro c e s s , H -C oal p ro c e s s , and v a rio u s Z in c C h lo rid e C a ta ly s t p ro cesse s [1 5 , 1 6 ].
S o lv e n t e x tra c tio n is th e liq u id phase d is s o lu tio n o f coal to liq u id s .
In t h is m e th o d , th e coal is p a r t ia lly d is s o lv e d in a h y d ro g e n r ic h s o l­
v e n t and th e u n d is s o lv e d p o rtio n is f ilt e r e d o u t.
T h e s o lv e n t is re c o ­
v e re d fro m th e p r o d u c t b y d is tilla tio n w h ile th e u n d is s o lv e d so lid is
re a cte d w ith steam to p ro d u c e h y d ro g e n .
T he se p ro cesse s a re g e n e ­
r a lly te rm e d as s o lv e n t re fin e d coal (S R C ).
T h e E xxon h y d ro g e n d o n o r s o lv e n t pro ce ss and th e C resap SRC
p ro ce ss a re exam ples o f th e s o lv e n t e x tra c tio n p ro c e s s .
In th e Exxon
m e th o d , a h y d ro g e n a te d h y d ro a ro m a tic m a te ria l is used as th e d o n o r
s o lv e n t a t o p e ra tin g c o n d itio n s o f 850°F and 200-1000 p s ig .
T h e y a re
o p e ra tin g a o n e -h a lf to n p e r d a y p ilo t p la n t in B a y to w n , T e x a s .
C re sa p SRC p ro ce ss r u n s a t 765°F and 150 p s ig .
F lo u r E n g in e e rin g is
o p e ra tin g a 20 to n p e r d a y p ilo t p la n t a t C re s a p , W est V ir g in a .
C re sa p p ro ce ss is also ca lle d P ro je c t G asoline.
The
The
G e n e ra lly th e liq u id
p ro d u c ts o f SRC p ro cesse s m u st be u p g ra d e d b y c a ta ly tic h y d ro g e n a ­
tio n
[1 7 ].
O th e r SRC processe s in c lu d e th e Pamco P ro ce ss, S o u th e rn
S e rv ic e s SRC Process and S o lv e n t R e fin e d L ig n ite P rocess [1 5 , 1 6 ].
14
P y ro ly s is o f coal in th e m ost g e n e ra l sense is th e h e a tin g o f coal
in th e absence o f o x y g e n and h y d ro g e n to c ra c k th e la rg e molecule's
in to sm a lle r liq u id and gaseous p r o d u c ts .
c a rb o n is re je c te d as a s o lid c h a r.
In th is p ro c e s s , m ost o f th e
T h e liq u id p ro d u c ts m u s t be f u r ­
th e re d u p g ra d e d to be in a u sa b le fo rm .
Examples o f coal p y r o ly s is
a re th e FMC COED p ro ce ss and O il S hale C o rp o ra tio n 's Toscoal P ro c e s s .
In th e COED m e th o d , coal is heated u s in g s u c c e s s iv e ly h ig h e r te m p e ra ­
tu r e s in a s e rie s o f f o u r flu id iz e d bed c a rb o n iz e rs .
P rocess p re s s u re s
a re fro m 5 to 10 p s ig w h ile p ro ce ss te m p e ra tu re s ra n g e fro m 500°F in
th e f i r s t c a rb o n iz e r to 1600°F in th e f o u r t h sta g e .
A 36 to n p e r d a y
COED p ilo t p la n t has been s u c c e s s fu lly ru n in P rin c e to n , New J e rs e y .
T h e p la n t has now been d is m a n tle d .
In th e Toscoal p ro c e s s , c ru s h e d
coal is p re h e a te d in a f lu id bed and th e n fe d to a p y r o ly s is d ru m
w h e re i t is heated b y h o t ce ra m ic b a lls .
densed and f r a c tio n a te d .
IOOO0F.
P y r o ly tic v a p o rs a re c o n ­
O p e ra tin g te m p e ra tu re s a re fro m SOO0F to
A 25 to n p e r d a y p ilo t p la n t has been ru n u s in g Wyoming
s u b -b itu m in o u s co a l.
O th e r p y r o ly t ic processe s in c lu d e th e H y d ro c a r-
b o n iz a tio n p ro c e s s , Seacoke p ro c e s s , and G a rr e tt Coal P y ro ly s is P ro ­
cess [1 5 , 1 6 ].
L iq u id h y d ro c a rb o n c a ta ly tic s y n th e s is can be a c h ie v e d u s in g
s y n th e s is gas v ia th e F is c h e r-T ro p s c h m e th o d . . In th is p ro c e s s , coal
is c o n v e rte d b y g a s ific a tio n to s y n th e s is gas (h y d ro g e n and ca rb o n
m o n o x id e ), w h ic h re a c t in th e p re se n ce o f a F is c h e r-T ro p s c h c a ta ly s t
15
to p ro d u c e a v a r ie t y o f liq u id p r o d u c ts .
t in g c o n d itio n s and ch o ice o f c a ta ly s t.
T h e y ie ld d e p e n d s on o p e ra ­
M ethanol can be p ro d u c e d
e x c lu s iv e ly b y c h o o sin g c o p p e r-z in c -c h ro m iu m c a ta ly s ts and s p e c ific
o p e ra tin g c o n d itio n s .
T h e F is c h e r-T ro p s c h p ro ce ss te c h n o lo g y has
been a v a ila b le co m m e rc ia lly f o r y e a rs as e v id e n c e d b y th e SASOL 8,000
to n p e r d a y p la n t o p e ra tin g in S o u th A f r ic a .
H ere coal is g a s ifie d v ia
th e Germ an L u r g i P rocess and liq u id p ro d u c ts are g e n e ra te d a t 300 to
360 psia and 430 to 660°F [1 5 , 1 6 ].
F.
S h o rt R esidence Tim e Coal L iq u e fa c tio n
R esearch s tu d y in g th e ra p id coal liq u e fa c tio n u s in g s h o r t re sid e n ce tim e
is b e in g s tu d ie d a t s e v e ra l lo ca tio n s a ro u n d th e U n ite d S ta te s .
re s e a rc h is g e n e ra lly d iv id e d in to tw o g e n e ra l c a te g o rie s :
The
( I ) n o n c a ta -
I y tic fla s h h y d r o p y r o ly s is (F H P ) and ( 2 ) ra p id c a ta ly tic h y d ro g e n a tio n .
T h e b asis o f th is re s e a rc h comes fro m th e p rem ise t h a t in th e
ra p id h e a tin g and h y d ro g e n a tio n , th e fo rm a tio n o f h ig h b o ilin g ta r s and
c h a r is p a r t ia lly e lim in a te d .
O n ly a s h o r t p e rio d o f tim e is a p p a re n tly
re q u ire d f o r th e liq u e fa c tio n o f c o a l; and i f th e liq u e fa c tio n p ro d u c ts
a re h e ld a t e le v a te d te m p e ra tu re s f o r lo n g e r p e rio d s o f tim e , no a d d i­
tio n a l c o n v e rs io n is o b ta in e d .
In f a c t, th e am ount o f u s e fu l p ro d u c ts
decrea ses th r o u g h p o ly m e riz a tio n and fo rm less u s e fu l p ro d u c ts such as
c h a r ( F ig u r e 5 ) [1 1 ].
R esearch p e rfo rm e d a t P e n n s y lv a n ia S ta te U n i­
v e r s it y shows t h a t coals g e n e ra te th e m ost v o la tile m a tte r y ie ld i f
Conversion, % of Coal
(Moisture-and-Ash-Free)
' ^ -P R O M P T -RESIDUE
20
40
60
Time, Minutes
F ig u re 5.
C o n v e rs io n o f Coal v s . Tim e o f R e a ctio n .
17
heated to re a c tio n te m p e ra tu re s a t e x tre m e ly h ig h ra te s .
I t a p p ears
th e s e h ig h ra te s p r e v e n t c r o s s - lin k in g p o ly m e riz a tio n w h ic h reduce s
th e y ie ld s o f th e d e s ira b le p ro d u c ts [1 8 , 1 9 ].
S h o rt re s id e n c e tim e (S R T ) coal liq u e fa c tio n is a f a i r l y new te c h ­
n o lo g y in w h ic h coal is r a p id ly h y d ro g e n a te d a t h ig h te m p e ra tu re and
p re s s u re and th e n q u e n ch e d to y ie ld a v a r ie t y o f p ro d u c ts in c lu d in g
s u b s titu te n a tu ra l g a s , an a ro m a tic d is tilla te o il composed o f m a in ly
b e n ze n e , to lu e n e , and x y le n e , a fu e l o il, s u lf u r , am m onia, and c h a r.
R esidence tim es a re g e n e ra lly fra c tio n s o f a second.
A m echanism has been p ro p o se d f o r th e h y d r o p y r o ly s is o f coal
in w h ic h i t is p o s tu la te d t h a t in th e in it ia l s ta g e s , d e co m p osition
re a c tio n s o c c u r as a f i r s t o r d e r c o n v e rs io n o f c a rb o n s o lid s to v o la tile
species t h a t flo w o u t o f th e s o lid in to th e b u lk gas flo w .
S ince th is
flo w is h ig h , th e r e is lit t le chance f o r h y d ro g e n to reach th e solid
in te rfa c e and re a c t d ir e c t ly .
In th e b u lk phase, th e v o la tile p ro d u c ts
o f coal d e co m p o sitio n re a c t f u r t h e r w ith th e h y d ro g e n .
A t h ig h te m ­
p e r a tu r e s , m o le cu la r c ra c k in g can o c c u r and fre e ra d ic a l p ro d u c ts are
s ta b liliz e d b y th e h ig h excess o f h y d ro g e n p re s e n t.
T h u s a lk y la te d
a ro m a tics w o u ld be d e a lk y la te d to fo rm benzene and m ethane and
r e s u lt in a h ig h y ie ld o f th e d e s ira b le o il p r o d u c t.
A t lo w e r te m p e ra ­
t u r e s , th e m o le cu la r c ra c k in g w o u ld o c c u r to a le sse r e x te n t and more
a lk y la te d species such as to lu e n e , x y le n e , p h e n o ls , and n a p h ta le n e s
w o u ld be in th e p r o d u c t [2 0 , 2 1 ].
R E LA TE D RESEARCH
A.
U n iv e r s ity o f U ta h 's C o n tin u o u s Coal H y d ro g e n a tio n Process
T h e U n iv e r s ity o f U tah has d e ve lo p e d a c o n tin u o u s c a ta ly tic fla s h
h y d ro g e n a tio n p ro c e s s u t iliz in g a t u b u la r re a c to r system fe e d b y a
s ta r wheel fe e d e r. . T h is d e s ig n uses a h ig h v e lo c ity , t u r b u le n t flo w ­
in g h y d ro g e n strea m to e n tr a in p u lv e riz e d coal and c a r r y i t th ro u g h a
p re s s u riz e d and hea ted tu b u la r r e a c to r .
T h e p ro ce ss em phasizes
s h o r t re s id e n c e tim e and s h o r t h y d ro g e n to coal r a tio s .
T h e p ro ce ss e q u ip m e n t c o n s is ts o f a p re s s u riz e d d u a l coal h o p p e r
and r o ta r y wheel fe e d e r , a h y d ro g e n -c o a l p a r tic le p r e h e a te r, a tu b u la r
re a c to r, a s o lid s - liq u id s r e c e iv e r, c o n d e n s e rs , a f i l t e r , and sam pling
and m o n ito rin g d e v ic e s .
T h e system can o p e ra te a t 2,000 p si a t a coal
feed ra te fro m 3 to 500 gram s p e r m in u te .
T h e p re h e a te r and f i r s t
re a c to r se ctio n a re im m ersed in m olten lead w h ile a fu rn a c e heats th e
re m a in in g p a r t o f th e re a c to r.
o f co ile d t u b in g .
T h e re a c to r c o n s is ts o f 2 0 -fo o t se ctio n s
R esidence tim e is v a rie d b y choice o f re a c to r le n g th .
A ty p ic a l ru n c o n s is ts o f a coal ra te o f 100 g /m in a t a h y d ro g e n flo w
ra te o f 30 s ta n d a rd c u b ic fe e t p e r m in u te w ith -40 mesh coal im p re g n a ­
te d w ith 5 .5 p e rc e n t d r y z in c c h lo rid e a t a te m p e ra tu re o f 550°F and
2,000 p s i.
T h e y have o b ta in e d c o n v e rs io n (M A E ) o f o v e r 40 p e rc e n t
f o r th e s e z in c h a lid e c a ta ly s ts [2 2 , 23, 2 4 ].
19
B.
C itie s S e rv ic e R esearch and D e ve lo p m e n t S h o rt R esidence Tim e
Coal H y d ro p y ro ly s is
In th e C itie s S e rv ic e FHP p ro c e s s , p u lv e riz e d coal (70 p e rc e n t
th r o u g h 200 m esh) is m ixed w ith p re h e a te d h y d ro g e n and fe d to a
re a c to r a t p re s s u re s ra n g in g betw een 600 and 3,000 p s ig and te m p e ra ­
tu r e s ra n g in g betw e en IIO O 0F and 1800°F.
t ic .
T h is p ro ce ss is n o n -c a ta ly -
C o a l-p a rtic le re s id e n c e tim e can be c o n tro lle d betw een 0.1 and 2
se co n d s.
A f t e r th e s h o r t re a c tio n , th e p ro d u c ts a re r a p id ly que n ch e d
b y flu s h in g w ith c r y o g e n ic a lly cooled h y d ro g e n .
T h e c h a r is s e p a ra ­
te d and th e gas strea m is cooled to cond ense b e n z e n e -to lu e n e -x y le n e
liq u id , o i l , ammonia liq u o r , and w a te r.
T h e re a c to r is a f r e e - f a ll p ip e heated b y an e le c tr ic fu rn a c e .
Coal is fe d b a tc h w is e in to a p re s s u riz e d h o p p e r w h e re a s ta r wheel
fe e d e r d e liv e rs th e coal and p re -h e a te d h y d ro g e n to th e re a c to r.
The
coal fa lls w ith th e h y d ro g e n th r o u g h a f o u r - f o o t p ip e - re a c to r d e v o la ­
t iliz in g along th e w a y .
T h e re s id e n c e tim e is c o n tro lle d b y in tr o d u c ­
tio n o f cold h y d ro g e n th r o u g h a v a ria b le le n g th p ro b e in s e rte d in to
th e bottom o f th e r e a c to r.
T h is allow s f o r c h a n g in g th e re a c to r le n g th
w ith o u t c h a n g in g th e r e a c to r.
p ip e .
T h e re a c to r is a 1% in c h sch e d u le d X X
T h e c o n d e n s in g system can be v a rie d fro m -2 0 0 °F to +200°F b y
use o f s u ita b le c o o la n ts .
T h e n o n -c o n d e n s a b le gases a re m e te re d ,
a n a lyze d b y gas c h ro m a to g ra p h y , and v e n te d .
T a b le I g iv e s a ra n g e
o f o p e ra tin g c o n d itio n s w h ic h ha ve been s tu d ie d .
W ith t h is syste m .
20
T a b le I.
C itie s S e rv ic e s Process Run C o n d itio n s
Run Tim e
1 .2 5 -8 .0 H r
H y d ro g e n /C o a l R atio
0 .1 8 -2 .0 I b /lb
A y g . P a rtic le Size
50-40 m icro n s
Coal H e atu p Rate
50,0 0 0 -1 5 0 ,0 0 0 ° F /s e c
A v g . R e a cto r T e m p e ra tu re
1150-1575°F
R e a cto r P re s s u re
500-3,000 psi
Q uench T e m p e ra tu re
450 -1OOO0F .
C itie s S e rv ic e s can p ro ce ss up to tw o p o u n d s o f coal p e r h o u r and
have r o u tin e ly a ch ie ve d coal c o n v e rs io n s o f 50 to 80 p e rc e n t [2 5 , 26,
2 7 ].
A n econom ic a n a ly s is o f a s c a le d -u p com m ercial p la n t u s in g t h is
p ro ce ss in d ic a te s t h a t a 14,124 TPD coal p la n t w ill consum e 838 TPD
o f h y d ro g e n w h ile p ro d u c in g 3,030 TP D m ethane, 840 TPO e th a n e , 982
TP D b e n z e n e -to lu e n e -x y le n e liq u id , 1,463 T p d c a rb o n m o n o xid e , 129
T P D am m onia, 2,265 TP D w a te r, and 6,072 TPD c h a r.
T h e c o st o f
su ch a p la n t is e stim a te d ( 1 s t q u a r t e r , 1977) to r e q u ir e a $ 1 .2 b illio n
c a p ita l in v e s tm e n t and 88 m illio n in a n n u a l o p e ra tin g c o s ts . . T h e gas
p ric e has been p r e lim in a r ily e stim ated to be betw een $2.66 and $3.09
21
p e r m illio n B tu f o r $ 5.00 p e r to n o f co a l.
T h is com pares w ith $3.49
p e r m illio n B T U f o r th e L u r g i p ro c e s s .
C.
S p e n c e r Chem ical C om pany Process
T h e S p e n c e r Chem ical C om pany FHP pro ce ss is a ra p id c a ta ly tic
h y d ro g e n a tio n m ethod f o r c o n v e rtin g coal to liq u id s .
P u lv e riz e d coal
is h y d ro g e n a te d a t te m p e ra tu re s ra n g in g fro m 900°F to IOOO0F and
1,500 to 2,000 p si w ith a re s id e n c e tim e o f less th a n one m in u te .
The
m ain p r o d u c t is a c ru d e a ro m a tic o il w h ic h can be f u r t h e r re fin e d to
g a s o lin e and lig h t o ils b y c o n v e n tio n a l te c h n iq u e s .
C a ta ly tic coal
and p re h e a te d h y d ro g e n a re fe d c o n tin u o u s ly in to a re a c to r w h e re
h y d r o p y r o ly s is o c c u rs .
s e p a ra te d .
T h e p ro d u c ts a re cooled r a p id ly and th e n
T h e m ethod o f fe e d in g was assumed to be e ith e r s ta r
wheel ty p e o r scre w ty p e and th e c a ta ly s t ty p e and am o u n t are p r o ­
p r ie t a r y .
A m a te ria l balance based on a s c a le d -u p p la n t in d ic a te d th a t
a p la n t u s in g 14,840 TP D o f coal and 325 TP D o f h y d r o g e n , w o uld p r o ­
du ce 1,610 TP D o f gas (h e a tin g v a lu e = 780 B t u / s c f ) , 8,383 TPD c ru d e
o il, and 1,840 TP D o f ash and c h a r .
P re lim in a ry econom ics in d ic a te
th is p la n t w o u ld r e q u ir e a c a p ita l in v e s tm e n t o f $205 m illio n a t an
a nn ual o p e ra tin g c o s t o f $30 m illio n .
F or $ 1 0 /to n o f coal a t 15 p e rc e n t
r e tu r n on in v e s tm e n t, th is is $1.36 p e r m illio n BTU
[2 8 ].
22
D.
B ro o k h a v e n N a tio n a l L a b o ra to ry FHP Process
R e se a rch e rs a t B ro o k h a v e n N a tio n a l L a b o ra to rie s a re s tu d y in g th e
p ro ce ss v a ria b le s and c h e m is try o f a ra p id gas p h a se , n o n -c a ta ly tic
fla s h h y d r o p y r o ly s is p ro c e s s .
T h e ben ch scale e x p e rim e n ta l e q u ip m e n t
is com posed o f a o n e -in c h dow n flo w e n tra in e d tu b u la r re a c to r d e sig n e d
to be o p e ra te d a t p re s s u re s u p to 4 ,000 p si and te m p e ra tu re s o f OOO0F
w ith a coal fe e d o f tw o p o u n d s p e r h o u r and h y d ro g e n fe e d o f one
p o u n d p e r h o u r.
O r ig in a lly coal was fe d to th e re a c to r w ith a r o ta ­
t in g c a v ity ty p e fe e d e r.
H o w e v e r, a s c re w ty p e has r e c e n tly been
in s ta lle d and used w ith b e tte r su cce ss.
h y d ro g e n p re h e a te r c o n s tru c te d fro m
I t was re p o rte d t h a t th e
In co n e l 601 had r u p tu r e d a fte r
18 h o u rs o f use a t 3,000 p si d ue to h y d ro g e n e m b rittle m e n t.
The
p re h e a te r was re p la c e d w ith Inconel 617 and has fu n c tio n e d o v e r 100
h o u rs w ith no p ro b le m s .
E x p e rim e n ta l re s u lts show th a t h y d ro c a rb o n y ie ld s in c re a s e to
60 p e rc e n t w ith p re s s u re up to a b o u t 3,000 p s i.
A t 750°C a b o u t o n e -
t h ir d o f th e y ie ld is liq u id w h ile a t 800°C th e y ie ld is e s s e n tia lly all
m ethane.
A t 3,000 p si and 800°C , gaseous p r o d u c t y ie ld in cre a se s
and liq u id p r o d u c t y ie ld decreases as th e re s id e n c e tim e is in cre a se d
fro m 2 .3 to 9 se co n d s.
F u r th e r te s ts show t h a t a t 7 5 0 °C , some decom ­
p o s itio n o f th e liq u id p r o d u c t ( b e n z e n e -to lu e n e -x y le n e ) o c c u rre d as
re s id e n c e tim e exceeded seven se co n d s.
A s th e re a c to r te m p e ra tu re
23
in c re a s e d , b o th th e ra te and e x te n t o f th e liq u id de co m p o sitio n in c re a ­
s e s.,
S tu d ie s p e rfo rm e d on s u b -b itu m in o u s coal r a th e r th a n lig n ite
show ed s im ila r p r o d u c t a n a ly s is e x c e p t th e in cre a se o f e th a n e in th e
gaseous p r o d u c t w ith s u b -b itu m in o u s coal [2 9 , 3 0 ].
E.
In s titu te o f Gas T e c h n o lo g y R is e r C ra c k in g o f Coal Process
In th e R is e r coal c r a c k in g p ro c e s s , n o n -c a ta ly tic coal is m etered
th r o u g h a c o n tin u o u s fe e d e r in to a h y d ro g e n c a r r ie r gas s tre a m .
m ix tu re is p re h e a te d b y r a d ia n tly hea ted coal to 1200°F .
T h e m ix ­
t u r e th e n e n te rs th e r is e r re a c to r tu b e and moves u p w a rd .
o x y g e n is in je c te d in to th e re a c to r and ig n itio n ta k e s p la c e .
b u s tio n s u p p lie s th e h e a t f o r th e c ra c k in g re a c tio n .
The
A ir o r
T h e com­
T h e com bustio n
ta k e s place in a t u r b u le n t ly flo w in g re g io n r a th e r th a n a flam e and
th u s is com pleted w ith in a fe w in c h e s o f th e o x y g e n in le t .
A t th e end
o f th e re a c to r, n itro g e n is bled in to in s u re co m b u stio n ceases and to
cool dow n th e p r o d u c ts .
T h e re a c ta n ts a re th e n c a r rie d to a s e p a ra to r
w h e re c h a r is d is e n tra in e d .
A w a te r c h ille d co n d e n s e r th e n se p a ra te s
o u t th e liq u id p ro d u c ts and th e gases a re an a lyze d b y o n - lin e gas c h r o ­
m a to g ra p h y .
A ben ch scale u n it has show n t h a t c a rb o n c o n v e rs io n in cre a se s u n i­
fo rm ly w ith in cre a se s in s e v e r ity o f th e rm a l tre a tm e n t.
A lso th e w e ig h t
24
fr a c tio n o f c h a r decrea ses u n ifo rm ly w h ile w e ig h t fr a c tio n gases and
liq u id s in c re a s e u n ifo r m ly w ith in c re a s in g s e v e r ity o f th e rm a l t r e a t ­
m e n t.
T h e w e ig h t fr a c tio n o f gases in cre a se s m ore s h a r p ly th a n th a t
o f liq u id s .
T h e u n it has been ru n p re d o m in a n tly a t 1800°F and 2,000
p s i, y ie ld in g s y n th e tic n a tu ra l g a s .
H o w e v e r, i t has been show n th a t
lo w e r te m p e ra tu re p y r o ly s is re s u lts in p ro d u c tio n o f liq u id p ro d u c ts .
C u r r e n t ly a la r g e r scale d e s ig n is b e in g fin a liz e d to p ro d u c e fu e l
ga se s, fu e l o il, and h ig h o cta n e m o to r g a s o lin e fro m a u n it p ro c e s s in g
100 I b / h r o f lig n ite coal and 12 I b / h r o f h y d ro g e n a t a te m p e ra tu re o f
1500°F and p re s s u re o f 2 ,000 p s ig .
T h e e x p e rim e n ta l in v e s tig a tio n
w ill d w e ll p r im a r ily on chan ges in o p e ra tin g p re s s u re and re sid e n ce
tim e [2 1 ].
Due to m echanical pro b le m s su ch as b r id g in g and s tic k in g in d e v i­
ces su ch as s ta r wheel fe e d e rs and s c re w fe e d e rs , a n o ve l m ethod o f
fe e d in g th e coal c o n tin u o u s ly to th e re a c to r was d e v e lo p e d .
The
m ethod used was to a e ra te th e s o lid s and m ete r them in to th e main
t r a n s p o r t lin e b y e n tra in e d flo w th r o u g h a small d ia m e te r o r ific e
( F ig u r e 6 ) .
Coal is ch a n n e le d in to a plenum cham ber b y a fu n n e l a t
th e b o ttom o f th e coal h o p p e r w h e re i t is e n tra in e d in a flo w o f gas
m o vin g th r o u g h th e plenum cham be r in to a o n e -e ig h th in c h d ia m e te r
o r ific e and e m p ty in g in to th e o n e -e ig h th in c h d ia m e te r m ain tr a n s p o r t
lin e .
25
4-in . DIAM
PRESSURE
EQUALIZER
LINE
SOLIDS METERING GAS
FEED HOPPER
CARRIER GAS
Cy O
MANOMETERS
3/4 -in .
DIAM
J rota-L
m eters
2-1/2 in.
l/8 -in . DIAM
l/8 -in . DIAM
AIR
SUPPLY
25 psi
F ig u re 6.
I n s titu te o f Gas T e c h n o lo g y S o lid F ee din g S ystem
[2 1 ]
26
P roblem s e n c o u n te re d w ith th e system w e re m a in ly d u e to s tic k in g
d ue to s ta tic e le c t r ic it y .
When th e coal was tre a te d w ith an a n ti- s ta tic
a g e n t, th e p ro b le m was g r e a tly d im in is h e d .
T h e fe e d ra te was c o r r e ­
la te d n ic e ly to th e s q u a re ro o t o f th e s u p e rfic ia l gas v e lo c ity in th e
e x it p o r t .
U n ifo rm and r e p ro d u c ib le fe e d ra te s are p ro d u c e d w ith m any
d if f e r e n t mesh sizes o f lig n ite coal [3 1 ].
F.
R ockw ell In te rn a tio n a l P a rtia l L iq u e fa c tio n FHP P rocess
T h e R ockw el I - R o c k e td y n e coal liq u e fa c tio n p ro ce ss is based on th e
p re m ise t h a t h ig h liq u id y ie ld s can be o b ta in e d b y ra p id m ix in g , ra p id
q u e n c h in g , fla s h p y r o ly s is .
P u lv e riz e d n o n -c a ta ly tic coal is in je c te d
in to th e re a c to r in a m ethod s im ila r to th e I n s titu te o f Gas T e c h n o lo g y
a p p ro a c h .
H o w e v e r, a r o c k e t e n g in e is used as th e in je c to r .
T h is
m ethod p ro v id e s f o r e x tre m e ly h ig h m ix in g , th u s re d u c in g th e problem
o f in s u ff ic ie n t ly re a c te d coal.
heated to 1200°F.
T h e coal is m ixed w ith h y d ro g e n p r e ­
R eaction re s id e n c e tim e s can be v a rie d fro m 10 to
1,000 m illis e c o n d s a t te m p e ra tu re s ra n g in g fro m 1500 to ISOO0F and
p re s s u re s o f 500 to 1,500 p s ig .
T h e re a c tio n p ro d u c ts a re q ue nched
w ith a w a te r s p r a y .
Phases in v o lv e d in t h is s tu d y in c lu d e a o n e - fo u r th to n p e r h o u r,
one to n p e r h o u r, and te n to n s p e r h o u r p ro ce sse s.
O v e ra ll carb o n
c o n v e rs io n s a re on th e o r d e r o f 50 p e r c e n t, 40 p e rc e n t b e in g liq u id
a
27
p r o d u c ts .
C o n v e rs io n s as h ig h as 64 p e rc e n t have been a c h ie v e d .
A
d e ta ile d tw o phase flo w model o f th e ro c k e t e n g in e in je c tio n fe e d e r
m ethod has also been done [3 2 , 3 3 ].
G.
O c c id e n ta l R esearch C o rp o ra tio n Flash P y ro ly s is System
T h e O c c id e n ta l R esearch C o rp o ra tio n 's fla s h p y r o ly s is system has
u n d e rg o n e se v e ra l b e n ch scale phases and is c u r r e n t ly o p e ra tin g as a
th re e to n p e r d a y coal c a p a c ity p ro ce ss d e ve lo p m e n t u n it .
The p ro ­
cess c o n s is ts o f fe e d in g m ille d n o n - c a ta ly tic coal b y means o f a screw
fe e d e r in to a p y r o ly s is re a c to r a t ra te s up to 300 p o u n d s p e r h o u r.
T h e coal is th e n m ixed w ith h o t re c y c le c h a r w h ich h e a t th e coal up
r a p id ly to a ro u n d 1200°F.
tim es th e coal fe e d ra te .
T h e c h a r re c y c le ra te is fro m fiv e to te n
A f t e r in it ia l h e a tu p , p ro ce ss h e a t is ge n e ­
ra te d b y c o m b u s tin g some o f th e re c y c le C har.
s e p a ra te d fro m th e c h a r in a se rie s o f c y c lo n e s .
is used to re c o v e r th e liq u id p r o d u c ts .
p ro c e s s .
P y r o ly tic v a p o rs are
A vacuu m fla s h u n it
No h y d ro g e n is used in th e
C a ta ly tic h y d ro g e n a tio n m ethods are b e in g s tu d ie d to
u p g ra d e th e t a r r y liq u id p r o d u c ts .
C u r r e n t re s u lts show t h a t th e p ro ce ss is te c h n ic a lly v ia b le o v e r
e x te n d e d p e rio d s o f tim e .
T a r d e riv e d fro m th e u n it show s ig n ific a n t
am ounts o f b e n z e n e -to lu e n e -x y le n e liq u id s and p h e n o ls .
A th e o re tic a l
model was d e ve lo p e d f o r th e d e v o la tiliz a tio n and c r a c k in g o f th e coal
[3 4 , 3 5 ].
C
28
H.
O th e r R esearch
O th e r s h o r t re s id e n c e tim e coal liq u e fa c tio n is b e in g done a t th e
C ity U n iv e r s ity o f New Y o r k , P itts b u r g E n e rg y R esearch C o rp o ra tio n ,
and M obile R esearch and D e ve lo p m e n t C o rp o ra tio n
I.
[2 7 , 3 8 ].
M ontana S ta te U n iv e r s ity R esearch
P re v io u s re s e a rc h a t MSU has show n metal c h lo rid e s to be a c tiv e
h y d ro d e n itro g e n a tio n c a ta ly s ts in th e p re s e n c e o f h y d ro g e n c h lo rid e
gas f o r tr e a tin g h e a v y C a lifo rn ia gas o ils [3 6 ].
T h is c o n c e p t was th e n
a p p lie d to th e b a tc h h y d ro g e n a tio n o f M ontana s u b -b itu m in o u s c o a l.
S e ve ra l metal c h lo rid e c a ta ly s ts im p re g n a te d on p u lv e r iz e d coal w ere
scre e n e d f o r h y d ro g e n a tio n a c t iv it y
[8 , 3 7 ].
A c o n tin u o u s t u b u la r re a c to r system was d e s ig n e d and b u ilt u s in g
th e s h o r t re s id e n c e tim e fla s h h y d ro p yro .lys.is p r in c ip le o f coal liq u e fa c ­
t io n .
T h e e ffe c ts o f te m p e ra tu re , p r e s s u r e , and flo w ra te on th e c o n ­
v e rs io n o f u n tre a te d coal in a h y d ro g e n atm o sphere w e re d e te rm in e d .
A ls o th e e ffe c t o f th re e metal c h lo rid e c a ta ly s ts on th e c o n v e rs io n o f
coal in a h y d ro g e n a tm o sp h e re was d e te rm in e d [ 7 ] .
T h e b asis th e n o f th is re s e a rc h is to use th e d u a l fu n c tio n a l
c a ta ly s t c a p a b ilitie s , i. e . acid to c a ta ly z e c ra c k in g and m etal to c a ta ly z e
h y d ro g e n a tio n , o f th e m etal c h lo rid e - h y d r o g e n c h lo rid e system in th e
c o n tin u o u s s h o r t re s id e n c e tim e liq u e fa c tio n o f M ontana s u b -b itu m in o u s
29
co a l.
I t is h y p o th e s iz e d t h a t th is system w ill r e s u lt in a h ig h c o n v e r­
sion o f coal to liq u id and gaseous p r o d u c ts .
A d v a n ta g e s o f th is system a re :
(1 )
S h o rt re s id e n c e tim e h y d r o p y r o ly s is g iv e s h ig h c o n v e rs io n
o f hexa ne s o lu b le liq u id p r o d u c t.
(2 )
T h e p ro ce ss e q u ip m e n t is in h e r e n tly sim p le .
(3 )
A s p h a lte n e p ro d u c ts can be m in im ize d .
(4 )
T h e c a ta ly s t system is a c tiv e in n itro g e n re m o va l.
i
RESEARCH O B JE C T IV E S
T h e o b je c tiv e s o f t h is re s e a rc h w e re :
(I)
T o o b ta in re lia b le and re p r o d u c ib le coal fe e d ra te data fro m
a c o n tin u o u s s ta r wheel fe e d e r.
(.2)
T o scre e n s ix d if f e r e n t m etal c h lo rid e c a ta ly s ts u s in g th e
c o n tin u o u s s h o r t re s id e n c e tim e coal liq u e fa c tio n p ro c e s s .
T h e c r it e r io n o f c o n v e rs io n w ill be used to c h a ra c te riz e
th e c a ta ly s ts in b o th h y d ro g e n and h y d ro g e n -h y d ro g e n
c h lo rid e fe e d gases.
(3 )
T o f u r t h e r c h a ra c te riz e th e c a ta ly s ts ' e ffe c tiv e n e s s b y ana­
ly z in g liq u id p ro d u c ts f o r n itro g e n and s u lf u r .
(4 )
T o d e te rm in e th e e ffe c t o f p r e s s u re , te m p e ra tu re , and c a r ­
r ie r gas flo w ra te on coal c o n v e rs io n .
M A T E R IA L S , EQ U IPM EN T, AN D PROCEDURES
A.
Process D e s c rip tio n
P u lv e riz e d coal is c h a rg e d b a tc h w is e to a coal fe e d e r w h e re i t is
c o n tin u o u s ly fe d b y a r o ta tin g s ta r w heel fe e d e r to a co ile d tu b e re a c ­
to r.
In th e fe e d e r, th e coal is e n tra in e d in th e flo w o f a c a r r ie r gas
w h ic h p ro p e ls th e coal th r o u g h th e re a c to r.
T h e p r o d u c t is co lle cte d
in a c o lle c tio n vessel and th e gas flo w is d e p re s s u riz e d , m e te re d , and
v e n te d to th e a tm o s p h e re .
S ince i t was p ro p o se d to use gaseous
h y d ro g e n c h lo rid e m ix tu re s as a c a r r ie r g a s , all in te r n a l e q u ip m e n t
p a r ts w e re made o f In co n e l w h e n e v e r p o s s ib le f o r re s is ta n c e to c o r r o ­
s io n .
B.
A p ro ce ss flo w s h e e t is show n in F ig u re 7.
Coal S ta r Feeder
A r o ta tin g coal s ta r fe e d e r was o b ta in e d fro m W. D . P eterson and
A sso cia te s o f M u r r a y , U tah ( F ig u r e 8 ) .
T h e fe e d e r was e q u ip p e d w ith
a s ta r s h a ft c o n s is tin g o f th re e c u b ic c e n tim e te rs o f vo lu m e p e r re v o ­
lu tio n .
T h e fe e d e r s h a ft was d r iv e n b y an e le c tric m o to r w ith a v a r i­
able speed o u tp u t w h ic h allow ed th e s h a ft speed to v a r y fro m 0 .2 to
3 .3 r e v o lu tio n s p e r m in u te ( F ig u r e 9 ) [ 7 ] .
T h e fe e d e r and h o p p e r u n it
w e re made o f In co n e l f o r c o rro s io n re s is ta n c e .
Coal Star F eeder
T emperature
Recorder
Nitrogen Purge L in e
T hermocouple
Needle
Valve
Reactor
Assembly
Ammeters
Powerstats
Back Pressure
Regulator
To Vent
Product
Co lle c t io n
Vessel
Wet T est Meter
Fi gur e 7.
Process
Ca u s t ic Scrubber
Flow Di agram
33
I >
Il
COAL .
HOPPER
PULLEY
THERMO­
COUPLE
WELL
ROTATING
STAR
IN L E T
•
ADD FLUID
INLET
C O A L FEED
(TO R EACTOR )
Figure 8.
Coal S tar Feeder.
34
Star Ca v it ie s
Figure 9.
Three Cubic Centimeter S tar Shaft.
35
C.
R e a cto r and H e a te r A sse m b ly
T h e re a c to r used in th is re s e a rc h c o n s is te d o f a le n g th o f V in c h
In co n e l 617 t u b in g , te n fe e t lo n g .
T h e re a c to r was co ile d a ro u n d a
3V1, V
T h e h e a v y w alled p ip e was used to
w a ll, s ta in le s s steel p ip e .
p r o v id e an a p p ro x im a te ly c o n s ta n t te m p e ra tu re h ea t s o u rc e f o r th e
re a c to r.
T h e re a c to r was e x te r n a lly in s u la te d w ith a b o u t s ix in ch e s o f
z o n a lite in s u la tio n ( F ig u r e 1 0 ).
Process h e a t was s u p p lie d to th e h e a v y w alled s ta in le s s steel p ip e
b y an im m ersion ty p e s t r ip h e a te r t h a t f i t in s id e o f i t .
Pow er was s u p -
lie d to th e s t r ip h e a te r b y p o w e rs ta ts co n n e cte d to 110 v o lt w all p lu g s .
I n - lin e am m eters m easured th e c u r r e n t g o in g to each o f th e th re e s tr ip s
o f th e h e a te r.
H e a tu p tim e f o r th is system was a b o u t o n e -h a lf h o u r to
b r in g th e re a c to r te m p e ra tu re up to 5 0 0 °C .
D.
P ro d u c t C o lle c tio n and S ystem P re s s u re
T h e p ro d u c ts w e re c o lle c te d in a P a rr S e rie s 4000 p re s s u re re a c ­
tio n a p p a ra tu s w h ic h was m o d ifie d to a c c e p t
V 1 S w age lock
f it t in g s .
T h is ve sse l is ra te d b y th e m a n u fa c tu re r to be sound to 10,000 p s i.
T h e c o p p e r head g a s k e t and a u to c la v e head w ere s e c u re d u s in g a
to rq u e w r e n c h .
New c o p p e r head g a s k e ts w e re to r q u e d to 60 f t - lb s and
up o n s u b s e q u e n t r u n s w e re to rq u e d h ig h e r in 10 f t - Ib in c re m e n ts u n til
100 f t - lb s was re a c h e d , w h e re u p o n a new g a s k e t was in s ta lle d .
S ilv e r
36
From Star F eeder
Co n ta in e r
I n s u la t io n
T hermocouple
St a in l e s s St e e l P ip e
( heavy
w a ll )
Tubular Reactor
St r ip Heater
To Product Co l l e c t io n V essel
Figure 10.
Reactor and Heater Detail.
37
Goop was used oh th e a u to c la v e cap b o lts to p r e v e n t s e iz u re a t h ig h
te m p e ra tu re s .
T h e system p re s s u re was m a in ta in e d b y a G ro ve M ig h ty M ite b ack
p re s s u re r e g u la to r .
T h e in te rn a l p a r ts o f th is d e v ic e w e re re -m a c h in e d
fro m in co n e l f o r th e p u rp o s e o f c o rro s io n re s is ta n c e .
A te flo n d ia ­
p h ra g m was used in th e p re s s u re r e g u la to r .
E.
T e m p e ra tu re M easurem ent and H y d ro g e n Flow M easurem ent
T h e re a c to r te m p e ra tu re was m easured u s in g a c h ro m e i-a lu m e l
th e rm o c o u p le c o n n e cte d to a s in g le p o in t H oneyw ell te m p e ra tu re re c o r d e r .
T h e th e rm o c o u p le was a tta c h e d to th e o u ts id e w all o f th e Inconel t u b u ­
la r re a c to r ( F ig u r e 7 ) .
T h e te c h n ic a l g ra d e h y d ro g e n gas was s u p p lie d fro m co m m e rcia lly
o b ta in e d , re g u la te d gas c y lin d e r s .
w e re p re p a re d as n e e d e d .
T h e h y d ro g e n c h lo rid e gas m ixes
H y d ro g e n c h lo rid e was a llow ed to flo w in to
an e v a cu a te d c y lin d e r u n t il th e d e s ire d s ta tic p re s s u re was re a ch e d .
T h e c y lin d e r was th e n pum ped w ith h y d ro g e n to th e d e s ire d to ta l p r e s ­
s u re w ith th e aid o f a Haskel Gas B o o s te r a ir - d r iv e n c o m p re s s o r.
T h e gas flo w ra te was c o n tro lle d b y a m icro m e te r v a lv e and mea­
s u re d d o w n stre a m b y use o f a w e t te s t m e te r.
38
F.
P re p a ra tio n and A n a ly s is o f Coal
Coal used in th is s tu d y was R o se b u d , M ontana, s u b -b itu m in o u s
coal s u p p lie d b y W estern E n e rg y C om pany in 1975.
T h e coal has been
s to re d in p la s tic lin e d d ru m s to p r e v e n t a n y d e c o m p o s itio n .
g iv e s th e p ro x im a te and u ltim a te a n a ly s is o f th e coal.
T a b le il
T h e c a rb o n to
h y d ro g e n r a tio is a b o u t 1 4 .5 .
T h e coal used in th e re s e a rc h was ta k e n fro m th e d ru m s and p u l­
v e riz e d in a b a ll m ill.
T h e coal was th e n screene d to -60 m esh.
coal was th e n s to re d in .p o ly e th y le n e bags to a w a it u se.
T h is
T h e coal was
n o t scre e n e d f u r t h e r and i t was d e cid e d to use th e to ta l -60 mesh coal
r a th e r th a n a n y fr a c tio n o f i t [ 7 ] .
A ll coal sam ples used in th is re s e a rc h w e re p r e d r ie d f o r f o r t y e ig h t h o u rs b e fo re b e in g c h a rg e d to th e coal h o p p e r.
done in a fo rc e d a ir oven a t 100°C .
T h e d r y in g was
T h e p u rp o s e o f th e d r y in g was
to im p ro v e th e fe e d in g c h a r a c te r is tic s o f th e coal [7 , 19, 2 6 ].
A ll
coal sam ples w e re tre a te d in a s im ila r m a n n e r to p r e v e n t a n y p o ssib le
a lte ra tio n s o f co m p o sitio n betw een sam ples.
39
T a b le IJ .
A n a ly s is o f th e C o ls trip S u b -b itu m in o u s C o a l.
P ro xim a te A n a ly s is
M o is tu re (a s re c e iv e d )
23.9%
V o la tile M a tte r ( M F )*
4 0 .6
F ixe d C a rb o n (M F )
4 9 .4
A sh (M F )
1 0.0
U ltim a te A n a ly s is (M F )
C a rb o n
66.1%
H y d ro g e n
4 .5
N itro g e n
0 .9
S u lfu r
0 .5
O xygen
1 8.0
A sh
10 .0
A n a ly s is o f M ajor A sh C om ponents
S iO 2
36.4%
A I20 S
1 7.6
Fe2O3
4 .6
T iO 2
0 .4
0 .8
P2 ° 5
CaO
2 2 .7
MgO
9 .4
Na2O
0 .3
K2O
0 .5
SO3
14 .9
* MF = m o is tu r e -fr e e basis
40
S ince c o n v e rs io n o f th e coal was d e te rm in e d on a m o is tu re and ash
fr e e b asis (M A P ), an a n a ly s is o f th e m o is tu re and ash in th e coal was
r e q u ir e d .
T h e m o is tu re a n a ly s is was com pleted im p le m e n tin g th e a p p a ­
ra tu s show n in F ig u re 11.
c h a rg e d to th e b o ilin g fla s k .
T o lu e n e and a w e igh ed am o u n t o f coal w ere
A s th e r is in g to lu e n e and w a te r v a p o r
c o n d e n s e d , i t fe ll in to th e g ra d u a te d re c e iv in g arm .
S ince w a te r has a
h ig h e r d e n s ity th a n to lu e n e , i t s e ttle d to th e bottom o f th e re c e iv in g
a rm .
T h e e q u ilib r iu m volum e o f w a te r p re s e n t in th e re c e iv in g arm
along w ith th e w e ig h t o f th e in itia l coal c h a rg e allow ed th e m o is tu re
c o n te n t o f th e coal to be c a lc u la te d .
T h is a n a ly s is was allow ed to ru n
f o r t w e n t y - f o u r h o u rs to in s u re t h a t all th e w a te r had been s trip p e d
fro m th e co a l.
T h e a n a ly s is was ru n on fre s h coal as w ell as coal
w h ic h had been d rie d f o r 48 h o u rs .
T h e ash c o n te n t o f th e coal was d e te rm in e d b y h e a tin g a w e igh ed
am oun t o f coal in a c o v e re d c r u c ib le w ith a bun sen b u r n e r .
A f t e r th e
v o la tile m a tte r had been d r iv e n o f f , th e c r u c ib le c o v e r was rem oved
and th e fix e d c a rb o n was b u rn e d a w a y.
T h e re m a in in g b ro w n is h
c o lo re d re s id u e was w e ig h e d and th e ash c o n te n t o f th e coal was c a lc u ­
la te d .
T h e se a n a lyse s w e re done u s in g random sam ples o f p u lv e riz e d coal
and i t is assum ed t h a t th r o u g h th e b a ll- m ill m ix in g , re p re s e n ta tiv e sam­
ples w e re g e n e ra te d .
41
Water I n ..
Water Out
Condenser
Graduated
Re c e iv e r
T oluene
Layer
Water
Layer
Bo i l i n g
Fl a s k
Powerstat
Water & T oluene
Figure 11.
Ma n tle
Apparatus Used to Determine Moisture Content of Coal.
42
G.
P re p a ra tio n o f C a ta ly tic Coal
In o r d e r to com pare th e a c tiv itie s o f th e metal c h lo rid e c a ta ly s ts ,
th e y had to be p re p a re d on an e q u iv a le n t' b a s is .
S ince p re v io u s c a ta ­
ly s t im p re g n a tio n w o rk had been done w ith n ic k e lo u s c h lo rid e , i t was
chosen as a re fe re n c e [ 3 7 ].
I t was d e cid e d to use a p p ro x im a te ly 3
w e ig h t p e rc e n t m etal on th e co a l.
T h re e p e rc e n t n ic k e l was chosen
sin ce i t was th e maxim um am ount w h ic h in aqueous s o lu tio n w o uld
s t ill w e t th e c o a l.
T h e coal was im p re g n a te d b y a d d in g a w e igh ed am oun t o f p re d rie d
coal to an aqueous s o lu tio n o f m etal c h lo rid e .
T h e aqu eous s o lu tio n s
w e re based on th e e q u iv a le n t am ounts o f m etal w h ic h w o u ld r e s u lt in a
3 p e rc e n t metal on coal w e ig h t r a tio .
O nce th e coal was added to th e
w a te r s o lu tio n , a g ita tio n was p ro v id e d u n t il th e coal was w e tte d .
The
m ix tu re was allow ed to s ta n d f o r t w e n t y - f o u r h o u rs w ith o n ly s p o ra d ic
a g ita tio n .
A t t h is tim e , th e e v a p o ra tio n ra te o f th e w a te r was in cre a se d
b y p la c in g th e m ix tu re in to a d r y in g oven a t 90°C .
T h e m ix tu re was
allow ed to s ta y in th e oven f o r f o r t y - e ig h t h o u rs to in s u re th a t all th e
w a te r o f h y d r a tio n associated w ith th e m etal c h lo rid e s w e re d r iv e n o f f .
T h e w e ig h t g a in o f th e d r ie d coal was a tte m p te d to be used to c a lc u la te
th e d e g re e Of c a ta ly s t im p re g n a tio n .
app e a re d to be in a c c u ra te .
H o w e v e r, t h is g r a v im e tr ic m ethod
T h u s th e d e g re e o f c a ta ly s t im p re g n a tio n
was c a lc u la te d in a m a n n e r s im ila r to th e coal ash a n a ly s is .
A w e igh ed
sam ple o f th e d r ie d , im p re g n a te d coal o f know n m o is tu re and ash
43
c o n te n t iyas hea ted in a c r u c ib le w ith a bun se n b u r n e r .
T h e v o la tile
m a tte r and fix e d c a rb o n w e re b u rn e d o f f le a v in g a re s id u e w h ich c o n ­
ta in e d o n ly ash and m etal c h lo rid e .
K n o w in g th e am oun t o f a sh , th e
p e rc e n t o f m etal c h lo rid e and th u s m etal on th e coal c o u ld be c a lc u la ­
te d .
T h e s ix m ost a c tiv e metal c h lo rid e c a ta ly s ts re p o rte d b y S ire in
1975 w e re used to im p re g n a te coal sam ples [3 7 ].
T h o se w e re n ic k e lo u s
c h lo rid e h e x a h y d ra te , sta n n o u s c h lo rid e p e n ta h y d ra te , c u p r ic c h lo rid e
d ih y d r a te , c o b a lt c h lo rid e h e x a h y d ra te , f e r r ic c h lo rid e f o u r - h y d r a te ,
and z in c c h lo rid e .
A ll w e re te c h n ic a l re a g e n t g ra d e s u p p lie d b y
F is c h e r S c ie n tific C om pany.
H.
P ro c e d u re f o r P e rfo rm in g a T e s t Run
A te s t ru n was s ta rte d b y c h a rg in g th e coal fe e d h o p p e r w ith an
am ount o f p re d r ie d co a l.
I t was fo u n d t h a t samples e x c e e d in g 1 ,000
gram s re s u lte d in th e m ost r e p ro d u c ib le fe e d ra te d a ta .
I t was also
fo u n d t h a t th e coal fe e d e r m u st be k e p t v e r y clean to g e t re p ro d u c ib le
fe e d ra te s .
T h is was done b y f r e q u e n t ly cle a n in g th e h o p p e r and r o ta ­
t in g s ta r s h a ft.
B e s t re s u lts w e re o b ta in e d w hen th e h o p p e r was
cleaned a t le a s t e v e r y o th e r r u n .
T h e c le a n in g p ro c e d u re in v o lv e d
v a c u u m in g o u t excess coal fro m th e p re v io u s r u n , and th e n th e s h a ft
was cleaned b y r u n n in g acetone a n d /o r to lu e n e th r o u g h th e fe e d in g
m echanism .
T h e re a c to r system was n o t a tta ch e d to th e fe e d e r d u r in g
44
th is s o lv e n t c le a n in g .
T h e s o lv e n t was rem oved b y b lo w in g com pressed
a ir th r o u g h th e .s y s te m and th e n allow ed i t to a ir d r y o v e r n ig h t.
A f t e r th e coal was c h a rg e d to th e h o p p e r, th e system was s lo w ly
p re s s u riz e d w ith n itro g e n to ru n p r e s s u r e , and th e p o w e r was tu rn e d
on to th e h e a tin g s y s te m .
D u rin g th e p re s s u riz a tio n p e r io d , th e s y s ­
tem was c lo s e ly exam ined f o r gas le a k s .
When system p re s s u re was re a c h e d , a small bleed flo w o f n itro g e n
was allow ed in o r d e r to p u rg e th e system o f a n y o x y g e n t h a t was p r e ­
s e n t.
T h is was done to m inim ize th e p o te n tia l and d a n g e ro u s problem
w h ic h e x is ts w hen o x y g e n and h y d ro g e n a re p re s e n t u n d e r p re s s u re
and a t h ig h te m p e ra tu re s .
C a re was ta k e n to p r e v e n t h ig h flo w ra te s
o f n itro g e n w h ic h co u ld a s p ira te u n re a c te d coal o u t o f th e h o p p e r and
in to th e p r o d u c t c o lle c tio n v e s s e l.
When th e re a c to r had reached th e
d e s ire d ru n te m p e ra tu re , th e n itro g e n was tu rn e d o f f and h y d ro g e n o r
h y d r o g e n - h y d r o g e n c h lo rid e was allow ed to flo w th r o u g h th e system .
T h e flo w ra te was a d ju s te d to th e d e s ire d v a lu e b y use o f th e m ic ro m e te rin g v a lv e and w e t te s t m e te r.
A t t h is tim e , a m b ie n t c o n d itio n s w e re re c o rd e d and th e fe e d e r was
s ta rte d to commence th e a ctu a l r u n .
D u rin g th e r u n , c a r r ie r gas flo w -
ra te and re a c to r te m p e ra tu re w e re m o n ito re d c o n tin u o u s ly .
Chan­
ges w e re made m a n u a lly to keep th e s e p a ra m e te rs a t th e d e s ire d ru n
c o n d itio n s .
T h e c a r r ie r gas flo w was a d ju s te d w ith th e m ic ro m e te rin g
v a lv e and th e re a c to r te m p e ra tu re was a d ju s te d b y v a r y in g th e p o w e r
45
s u p p lie d b y th e p o w e rs ta ts to th e h e a tin g syste m .
S ince th e c a r r ie r
gas was n o t p re h e a te d and th e flo w ra te s used w e re la rg e , a s ig n if i­
c a n t ch a n g e in te m p e ra tu re co u ld o c c u r d u e to a r e la tiv e ly small
cha n g e in flo w ra te .
C a re was ta k e n to in s u re th a t flo w ra te s , and
th u s te m p e ra tu re s d id n o t v a r y s ig n if ic a n tly .
T h e flo w ra te was m easured d o w n stre a m fro m th e re a c tio n system
and i t is assum ed in th is re s e a rc h t h a t th e h y d ro g e n flo w g r e a tly
exceeds th e h y d ro g e n consum ed a n d /o r th e gaseous p ro d u c ts p r o ­
duced.
flo w r a te .
T h u s th e flo w ra te m easured is e s s e n tia lly th e to ta l c a r r ie r gas
I t s h o u ld be n oted t h a t no a tte m p t was made to e va lu a te
e ith e r th e e x te n t o r q u a lity o f th e gases p ro d u c e d b y th e re a c tio n .
A f t e r th e r u n had been allow ed to p rocee d f o r a d e s ig n a te d
p e rio d o f tim e , u s u a lly o n e -h a lf h o u r , th e system was d e p re s s u riz e d
and th e c o n te n ts o f th e p r o d u c t c o lle c tio n vessel was rem oved and a na­
lyze d f o r c o n v e rs io n and f o r n itro g e n and s u lfu r c o n te n t.
I.
D e te rm in a tio n o f C o n v e rs io n
T h e d e te rm in a tio n o f c o n v e rs io n was done on th e b a sis o f th re e
s o lv e n t e x tr a c tio n s .
T h e p r o d u c t c o lle c te d fro m th e re a c to r was f i r s t
e x tra c te d w ith c y c lo h e x a n e y ie ld in g th e o il p r o d u c t.
T h e second
e x tra c tio n was done w ith to lu e n e w h ic h y ie ld e d th e a s p h a lte n e p r o d u c t,
and th e la s t e x tra c tio n was done u s in g p y r id in e y ie ld in g th e a s p h a lto l
c o n te n t o f th e p r o d u c t [ 7 ] .
T h e to ta l c o n v e rs io n was ta k e n as th e
46
sum o f th e th re e in d iv id u a l c o n v e rs io n s .
T h e e x tra c tio n s w e re made
u s in g th e aid o f a S o x h le t e x tra c tio n a p p a ra tu s ( F ig u r e 1 2 ).
T h e p r o d u c t rem oved fro m th e p r o d u c t c o lle c tio n vessel was
w e ig h e d to d e te rm in e coal fe e d ra te and th e n a p o rtio n was w eighed
and placed in a d o u b le th ic k n e s s p r e d r ie d c e llu lo s e e x tra c tio n th im b le
(40mm x 120mm ).
T h e th im b le and sam ple w e re th e n p laced in th e
e x tra c tio n a p p a ra tu s ( F ig u r e 1 2 ).
T h e s o lv e n t v a p o r fro m th e b o ilin g
fla s k rose th r o u g h th e sid e arm and up to th e c o n d e n s e r w h e re i t
cond ensed and fe ll in to th e th im b le .
When th e s o lv e n t h e ig h t reached
th e u p p e r le vel o f th e s ip h o n a rm , i t was sip h o n e d th r o u g h th e th im ­
b le and b a c k in to th e b o ilin g fla s k .
A n y s o lu b le m a te ria l in th e sam ple
w o u ld th e n be c a r rie d w ith th e s o lv e n t, th ro u g h th e th im b le and b a ck
to th e fla s k .
T h e e x tra c tio n p ro c e d u re was allow ed to p ro g re s s u n til
th e s o lv e n t flo w in g th r o u g h th e w a lls o f th e th im b le was c le a r.
T h e th im b le and th e sam ple re s id u e w e re rem oved fro m th e a p p a ra ­
tu s and allow ed to a ir d r y a fte r each e x tra c tio n was fin is h e d . , T h e th im
b le was th e n placed in a d r y in g oven a t IOO0C f o r t w e n t y - f o u r h o u rs .
I f a n y p r o d u c t d e g ra d a tio n o r co m p o sitio n changes o c c u rre d as a r e s u lt
o f th is p ro c e d u re , i t is assum ed to ha ve been c o n s is te n t as all samples
w e re tre a te d in a s im ila r fa s h io n .
w e ig h e d .
A f t e r th e th im b le was d r ie d , i t was
T h is p ro c e d u re was re p e a te d f o r th e same sam ple in th e
o th e r tw o s o lv e n ts .
U n re a c te d coal was also a n a lyzed f o r o il, a s p h a l­
te n e , and a s p h a lto l c o n v e rs io n .
47
Water Out
Condenser
Water I n
Ex t r a c t io n
Ex t r a c t io n
T ube
T h im b l e
So lvent
-
Bo il in g
F lask
To Powerstat
Ma n tle
F ig u re 12.
S o x h le t E x tr a c tio n A p p a ra tu s Used to D e te rm in e Coal
C o n v e rs io n .
48
In m a kin g th e c o n v e rs io n c a lc u la tio n , th e d iffe r e n c e in sample
w e ig h ts b e fo re and a f te r th e e x tra c tio n was ta k e n to be th e am ount o f
p r o d u c t c o n v e rte d to O il, a s p h a lte n e , o r a s p h a lto l.
B y k n o w in g th e
a s h , m o is tu re , and c a ta ly s t c o n te n t, th e m o is tu re , a s h , and c a ta ly s t
fr e e (IVIACF) c o n te n t o f th e o r ig in a l sam ple co uld be c a lc u la te d .
The
w e ig h t loss b y e x tra c tio n w o u ld y ie ld th e c o n v e rs io n to th e v a rio u s
p ro d u c ts b y th e fo llo w in g e q u a tio n :
C
=
( l/M A C F ) x 100% - V
or
C
=
( l/M A F ) x 100% - V
f o r n o n - c a ta ly tic c o a ls, w h e re
C
= % c o n v e rs io n o f coal to th e re s p e c tiv e p r o d u c t f o r
each s o lv e n t,
MAF
= w e ig h t o f m o is tu re and ash fro m m a te ria l p re s e n t in
th e sam ple,
M ACF
= w e ig h t o f m o is tu re , a s h , and c a ta ly s t fr e e m ate rial
p re s e n t in th e sam ple,
I
= w e ig h t loss d u r in g e x tr a c tio n ,
V
= p e rc e n ta g e o f s o lu b le s p re s e n t in u n re a c te d coal f o r
t h a t s o lv e n t.
T h e c o n v e rs io n th e n g iv e s a re p re s e n ta tio n o f how th e coal has
been u p g ra d e d .
T h e to ta l c o n v e rs io n is th e sum o f th e in d iv id u a l c o n ­
v e rs io n s f o r th e same sam ple.
49
I t is im p o rta n t to n o te h e re t h a t th e c o n v e rs io n to gaseous p r o ­
d u c ts was n o t s tu d ie d .
No means w e re ta k e n to q u a n tify th e am ount
o f gases p ro d u c e d in th e re a c tio n and o n ly th e c o n v e rs io n o f liq u id
p ro d u c ts is r e p o r te d .
J.
S u lf u r and N itro g e n D e te rm in a tio n
T h e p ro d u c ts fro m all ru n s w e re a n a lyze d f o r s u lf u r and n itro g e n
c o n te n t as w ell as c o n v e rs io n to f u r t h e r c h a ra c te riz e th e a c t iv it y o f
th e c a ta ly s ts .
S u lf u r a n a lyse s w e re p e rfo rm e d b y th e q u a rtz tu b e com bustion
m ethod u s in g a B ic o -B ro w n S hell d e s ig n s u lf u r a p p a ra tu s ( ASTIVI
D -155 1) [3 9 ].
N itro g e n c o n te n t was d e te rm in e d b y th e M a c ro -K je ld a h l m ethod
(A S T M E -258) [4 0 ].
T h e te m p e ra tu re o f d ig e s tio n was im p o rta n t
in o b ta in in g good re p ro d u c ib le r e s u lts .
S u lf u r and n itro g e n c o n te n t o f th e p r o d u c t oil and a sp h a lte n e
w e re also d e te rm in e d f o r a fe w sam ples.
RESULTS AND DISCUSSION
A.
Coal A n a ly s is
A sh a n a ly s is was done a t th e b e g in n in g o f th is re s e a rc h on p u l­
v e riz e d coal and used f o r c a lc u la tio n p u rp o s e s th r o u g h o u t.
T h e p u l­
v e riz e d coal was assum ed to be w ell m ix e d , as d u p lic a te , ra n d o m ly
p ic k e d sam ple y ie ld e d re p ro d u c ib le re s u lts o f 9 .4 p e rc e n t a s h .
T h is
v a lu e c o rre s p o n d s c lo s e ly w ith p re v io u s o th e r lite r a t u r e re p o r ts f o r
R osebud coal [8 , 4 1 ].
Coal was also a n a lyze d f o r m o is tu re c o n te n t b o th b e fo re and
a fte r d r y in g .
T h e u n d rie d coal was fo u n d to have a m o is tu re level
o f 20.1 p e rc e n t.
T h is again c o rre s p o n d s to lite r a tu r e va lu e s o f
2 0 .3 p e rc e n t and 2 3 .9 p e rc e n t [7 , 4 1 ].
P re v io u s re s e a rc h has show n t h a t p u lv e riz e d coal show s a much
g r e a te r te n d e n c y to feed u n ifo rm ly w hen i t has been p r e d r ie d
2 1 ].
[7 , 19,
In th is re s e a rc h , g u id e lin e s s e t in a p re v io u s s tu d y w e re fo llo w e d .
T h e coal a p p e a rs to re a ch an e q u ilib r iu m d r y in g tim e o f f o r t y - e ig h t
h o u rs w hen k e p t in an ove n a t 100°C .
T h is tim e was d e fin e d as when
th e tim e d e r iv a tiv e o f th e coal w e ig h t ch a n g e reached z e ro [ 7 ] .
W ater
a n a ly s is on th e d r ie d coal show ed t h a t 0 .5 p e rc e n t m o is tu re rem a ine d.
T h e s to ra g e , p u lv e r iz in g and d r y in g o f th e coal used in th is
re s e a rc h co u ld have a ffe c te d its a b ilit y to be liq u if ie d .
A g in g o f coal
has been show n to re d u c e its a c t iv it y d u e to o x id a tio n o f th e s u rfa c e ..
W ork done a t th e B u re a u o f M ines show ed th e coal aged f o u r weeks in
51
th e open e n v iro n m e n t d ro p p e d fro m 90 p e rc e n t to 77 p e rc e n t c o n v e r­
s io n .
yvhen th e coal was d rie d a t 105°C f o r one d a y , th e c o n v e rs io n
d ro p p e d to 54 p e rc e n t.
T h e y also show ed t h a t th e c o n v e rs io n was a
fu n c tio n o f th e coal m o is tu re c o n te n t [4 2 ].
O th e r re p o r ts also show t h a t coal w ili o x id iz e in a ir and change
th e am oun t o f v o la tile m a tte r a v a ila b le .
T h e coal p a r tic le size is an .
im p o rta n t c r it e r ia f o r th e a c c e s s ib ility o f o x y g e n [ 7 ] .
T h e se tr e n d s show t h a t b o th th e d r y in g and p u lv e r iz a tio n o f th e
coal used in th is re s e a rc h co u ld ha ve a d e trim e n ta l e ffe c t on c o n v e r­
s io n .
B o th p ro cesse s a llow o x y g e n to be in c o n ta c t w ith th e coal.
It
is assum ed, h o w e v e r, t h a t i f th e s e e ffe c ts a re o c c u r r in g , i t w ill be
c o n s is te n t th r o u g h o u t sin ce all sam ples w e re tre a te d in a lik e m a nne r.
Coal c o n v e rs io n s w e re m easured on th e basis o f th r e e s o lv e n t
e x tr a c tio n s :
c y c lo h e x a n e , to lu e n e , and p y r id in e .
T h e p ro d u c ts o f th e
e x tra c tio n s a re o i l, a s p h a lte n e , and a s p h a lto l r e s p e c tiv e ly .
T h is
m ethod o f a n a ly s is was chosen d u e to its a b ility to m ore a c c u ra te ly
d e s c rib e th e p ro d u c ts o f coal liq u e fa c tio n
[7 , 9, 13, 14, 3 8 ].
Much o f
th e b a sic re s e a rc h done on th e s e s o lv e n t e x tra c tio n s was done u s in g
benzene in place o f to lu e n e .
H o w e v e r, i t has been show n th a t to lu e n e
can be s u b s titu te d w ith o u t a n y s ig n ific a n t d iffe re n c e s [1 2 , 4 3 ].
U n re a c te d coal was te s te d f o r o il, a s p h a lte n e , and a s p h a lto l c o n ­
t e n t and was fo u n d to c o n ta in 0 .4 p e rc e n t o il, 0 .2 p e rc e n t a s p h a lte n e ,
and 0.1 p e rc e n t a s p h a lto l f o r a to ta l o f 0 .7 p e rc e n t to ta l c o n v e rs io n .
52
No coal p a r tic le size d is tr ib u tio n s tu d ie s w e re don e a lth o u g h i t
seems p o s s ib le t h a t t h is p a ra m e te r c o u ld be o p tim iz e d .
I t has been
show n th e coal c o n v e rs io n decreases w ith a decrease in th e a verag e
p a r tic le size .
T h is means t h a t th e s m a lle r p a rtic le s a re c a rrie d th r o u g h
th e re a c to r fa s te r and th u s a re n o t in th e h o t zone lo ng enough to be
heated to re a c tio n te m p e ra tu re [2 2 ].
I t is also re p o rte d t h a t coal can
be fe d m ore u n ifo rm ly and r e p r o d u c ib ly w ith sm a lle r p a r tic le size coal
[1 9 , 22, 2 6 ].
B.
C old Flow F e e d ra te T e s ts
S ince p re v io u s re s e a rc h a t t h is U n iv e r s ity on th e same e x p e r i­
m ental e q u ip m e n t re s u lte d in v e r y low and n o n -u n ifo rm coal fe e d ra te s , an a tte m p t was made to u n d e rs ta n d t h is p ro b le m m ore f u ll y .
A
com pariso n o f th e MSU o p e ra tin g p a ra m e te rs was done w ith a n o th e r s im i­
la r p ro ce ss o p e ra tin g a t th e U n iv e r s ity o f U tah [2 2 , 2 3 ].
T h is r e s u l­
te d in th e p re m ise t h a t h ig h e r c a r r ie r gas flo w ra te s w e re needed to
o b ta in h ig h coal fe e d r a te s .
T h e U n iv e r s ity o f U tah o p e ra te d w ith a
gas re a c to r re s id e n c e tim e a b o u t te n tim es less th a n p re v io u s re se a rch
done a t M SU .
T h e p a r tic le re s id e n c e tim e is n o t th e same as gas r e s i­
dence tim e d ue to f r ic t io n and th e te n d e n c y f o r p a r t ia lly liq u e fie d ,
s t ic k y coal p a rtic le s to a g g lo m e ra te and s tic k to th e w a lls o f th e re a c ­
to r.
53
T h is lead to a p ro g ra m to o b ta in coal fe e d ra te d a ta a t v a rio u s d i f ­
f e r e n t c a r r ie r gas flo w ra te s in w h ic h a b o u t 25 ru n s w e re made.
T he se
co ld flo w te s ts w e re done u s in g o p e ra tin g c o n d itio n s show n in T a b le I I I .
T a b le I I I .
C old Flow T e s tin g O p e ra tin g P aram eters
C a r r ie r Flow Gas
N itro g e n
R e a cto r P re s s u re
500 p s ig
R e a cto r T e m p e ra tu re
A m b ie n t
Run Tim e
20 m in u te s
Coal Feed
-50 mesh
d rie d
c a ta ly tic
T h e re s u lts o f th e s e cold flo w fe e d ra te te s ts a re show n in F ig u re
13.
I t can be seen t h a t u n d e r th e s e o p e ra tin g c o n d itio n s , th e coal
fe e d ra te in c re a s e s u n ifo r m ly w ith c a r r ie r gas flo w ra te .
A s a r e s u lt o f
t h is t e s t , i t was d e cid e d to ru n a t 30 s c fh (s ta n d a rd c u b ic fe e t p e r
h o u r ) as a s ta n d a rd ru n c o n d itio n .
A n o th e r o p e ra tin g v a ria b le was re c o g n iz e d as b e in g a ffe c te d b y
th e ch a n g e to in c re a s e d c a r r ie r gas flo w r a te .
S ince th e c a r r ie r gas
was n o t p re h e a te d in th is re s e a rc h , th e laws o f h e a t t r a n s f e r p r e d ic t
t h a t w ith in c re a s e d flo w r a te , i t w ill r e q u ir e m ore tim e f o r th e gas to
be heated to re a c tio n te m p e ra tu re .
A th e o re tic a l h e a t t r a n s f e r a n a ly s is
54
Ca r r ie r Gas F low,
F ig u re 13.
sc f h
T h e E ffe c t o f C a r r ie r Gas F lo w ra te on Coal F e e d ra te .
55
m o d e lin g th e system as a d o u b le p ip e h e a t e x c h a n g e r w ith a heated
le n g th o f s ix fe e t and a c o n s ta n t w all te m p e ra tu re o f 500°C showed
t h a t th e gas to o k up to h a lf th e le n g th to be heated to re a c tio n te m ­
p e r a tu r e .
In p r a c tic e , th is model was c o n s e rv a tiv e s in c e th e w all te m -
p e a tu re w o u ld d ro p w hen h ig h flo w ra te s o c c u r r e d .
T h u s th e ,actual
re a c tio n te m p e ra tu re s a re som ew hat less th a n th e te m p e ra tu re m easured
on th e w all o f th e re a c to r.
C.
P re lim in a ry R esearch
P re lim in a ry re s e a rc h was done to show t h a t th e e q u ip m e n t was
o p e ra b le a t h ig h e r flo w ra te s and to re p ro d u c e some p re v io u s d a ta .
T h e m ost im p o rta n t o p e ra tin g v a ria b le a ffe c te d b y th e in c re a s e d flo w ra te was th e re a c to r te m p e ra tu re .
Small changes in flo w ra te w ould
cause th e te m p e ra tu re to flu c tu a te fro m th e d e s ire d ru n v a lu e .
F re ­
q u e n t a d ju s tm e n ts w e re re q u ire d to keep th e te m p e ra tu re close to th e
d e s ire d o p e ra tin g v a lu e .
P re lim in a ry ru n s p e rfo rm e d w ith n o n -c a ta ly tic coal u s in g h y d ro g e n
as th e c a r r ie r gas show ed r e p r o d u c ib ilit y o f th e coal fe e d ra te and th e
v ia b ilit y o f g e ttin g coal c o n v e rs io n a t h ig h e r fe e d ra te s .
n a r y r u n da ta is show n in T a b le IV .
th e s e p r e lim in a r y r u n s .
Some p r e lim i­
T a b le V shows th e re s u lts o f
56
T a b le : IV .
Run
Some P re lim in a ry R e su lts
A v g . Run
Run
T em p.
P re s s u re
(°c)
P ro d u c t
T o ta l
H2
F lo w ra te
C o lle c tio n Rate
C o n v e rs io n
( p s ig )
( s c fh )
(g /h r)
(%)
— — —
— — —
0 .7
EO*
— -------
— — —
El
470
1,000
40
68
14.0
E2
450
1,000
38
68
11.9
ES
455
800
39
67
6 .0
E4
460
1,000
26
19
7 .2
ES
470
500
39
60
2 .7
* EO re p re s e n ts u n re a cte d coal
T a b le V .
F u r th e r R e su lts o f P re lim in a ry R esearch
C o n v e rs io n
%
%
Run
O il
A s p h a lte n e
A s p h a lto l
S u lf u r
N itro g e n
EO
0 .4
0 .2
0.1
.57
1 .0 3
El
13.1
0 .6
0 .3
.41
1.13
E2
9 .0
2.1
0 .8
.63
1.10
ES
5 .8
0.1
0.1
.46
1.16
E4
. 6 .7
0 .4
. 0.1
9
1.15
ES
2.1
0 .5
0.1
.57
1.05
57
A s a r e s u lt o f th is re s e a rc h , th e s ta n d a rd ru n c o n d itio n s w ere
chosen f o r th e re m a in d e r o f th e re s e a rc h .
T he se c o n d itio n s w ere used
in th e c a ta ly tic s c re e n in g re s e a rc h and w e re th e basis o f th e w o rk done
to d e te rm in e th e e ffe c t o f te m p e ra tu re , p re s s u re and flo w ra te .
In
th e s e t e s t s , th e v a r ia b le b e in g te s te d was a lte re d fro m its s ta n d a rd
c o n d itio n .
T a b le V l show s th e s ta n d a rd ru n c o n d itio n s .
T a b le V I.
S ta n d a rd Run C o n d itio n s
T e m p e ra tu re
500°C
P re s s u re
1,000 p s ig
C a r r ie r Gas F lo w ra te
30 s c fh
R e acto r L e n g th
6 ft
Coal Feed
-50 mesh
im p re g n a te d c a ta ly tic
Run Tim e
D.
30 m in u te s
T h e E ffe c t o f C a ta ly s is on Coal C o n v e rs io n
T h e s ix m ost a c tiv e metal c h lo rid e s d e te rm in e d b y S ire (1975)
[ 3 7 ] , along w ith n o n - c a ta ly tic coal w e re te s te d a t s ta n d a rd c o n d itio n s
f o r coal c o n v e rs io n and p r o d u c t s u lf u r and n itro g e n c o n te n t.
T hese
c a ta ly s ts w e re im p re g n a te d o n to d r ie d , p u lv e riz e d coal fro m aqueous
s o lu tio n .
T o com pare th e c a ta ly s ts on ah e q u iv a le n t b a s is , th re e p e r ­
c e n t m etal on coal was chosen as th e c a ta ly s t c o n c e n tra tio n .
T h e c a ta ­
ly s ts used and coal c a ta ly s t c o n c e n tra tio n s are show n in T a b le V I I .
58
T a b le V I L
M etal C h lo rid e C a ta ly s ts and Coal C o n c e n tra tio n s
M etal C h lo rid e
% Metal on Coal
N iC I2 1SH2O
2 .8 6
S n C I2 1EH2O
2.2 0
Z n C I2
2.9 7
C u C I2 - 2H20
2.8 3
CoCI2 1SH2O
3.2 0
FeCI2 "4H 20
2 .40
T h e c a ta ly s ts w e re im p re g n a te d b y d is s o lv in g th e e q u iv a le n t
am oun t o f h y d ra te d c h lo rid e such t h a t th e am ount o f m etal w o u ld be
3 p e rc e n t o f 1,000 gram s o f coal.
F o r h y d ra te d n ic k e l c h lo rid e , 121.5
gram s w e re used to make th e aqueous s o lu tio n .
A ll o f th e w a te r was
th e n d r iv e n o f f y ie ld in g th e im p re g n a te d c a ta ly tic co a l.
T h e coal was
th e n d r ie d a t IOO0C to d r iv e o f f all th e w a te r o f h y d r a tio n
[7 ] and
in s u re t h a t th e c h lo rid e s e x is te d in th e n o n -h y d ra te d fo rm .
T h e e x p e rim e n ta l r u n s w e re done in o r d e r o f in c re a s in g c a ta ly s t
v o la t ilit y to m inim ize th e e ffe c t o f a h ig h ly v o la tile c a ta ly s t co a tin g
th e re a c to r w all and a ffe c tin g th e s u b s e q u e n t r u n s .
T h e re s u lts o f th e s e c a ta ly s t te s ts along w ith th e re s u lts o f n o n c a ta ly tic coal a re show n in T a b le V l l i f o r ru n s made w ith h y d ro g e n
a t s ta n d a rd c o n d itio n s .
T a b le IX show s th e c o n v e rs io n s b ro k e n dow n
in to th e in d iv id u a l fr a c tio n s .
59
T a b le V I I I .
T h e E ffe c t o f Metal C h lo rid e C a ta ly s ts on Coal C o n v e rs io n
C a ta ly s t
T o ta l C o n v e rs io n
% S u lfu r
% N itro g e n
Z n C I2
24.0%
0.61
1.13
S n C I2
17.2%
0.55
1.10
C u C I2
16.5%
0.5 7
N iC I2
15.5%
0 .5 2
1.14
CoCI2
10.8%
0.51
1.03
FeCI2
8.3%
0.61
1.00
N o n -c a ta ly tic
4.2%
0.7 9
1.10
U n re a c te d Coal
0.7%
0.57
1.03
T a b le IX .
-------—
T h e E ffe c t o f Metal C h lo rid e C a ta ly s ts on In d iv id u a l Coal
C o n v e rs io n
C o n v e rs io n
O il
A s p h a lte n e
A s p h a lto l
T o ta l
Z n C I2
16 .9
6.1
1 .0
24 .0
S n C I2
14 .3
2 .9
0 .0
17.2
C u C I2
13.0
2 .8
0 .7
16.5
N iC I2
14.0
1 .5
0 .0
15.5
C oC I2
9 .9
0 .9
0 .0
10.8
FeCI2
5 .7
1 .9
0 .7
8 .3
N o n -C a ta ly tic
3 .8
0 .3
0.1
4 .2
U n re a c te d
0 .4
0 .2
0.1
0 .7
C a ta ly s t
.
60
I t is n o te d t h a t all o f th e c a ta ly s ts in c re a s e th e coal c o n v e rs io n ,
u p to a fa c to r o f s ix fo ld o v e r n o n -c a ta ly tic coal.
R e su lts o f c a ta ly tic ru n s show c o n v e rs io n s less th a n re p o rte d in
p re v io u s c a ta ly tic s tu d ie s u s in g th e same e q u ip m e n t [ 7 ] .
T h e most
p ro b a b le reason f o r t h is is t h a t th e use o f h ig h flo w ra te s in th is
re s e a rc h te n d e d to re d u c e th e a c tu a l re a c tio n te m p e ra tu re fro m w h a t
was re c o rd e d .
T h is lo w e r c o n v e rs io n th e n a p p a re n tly is a r e s u lt o f
lo w e r o p e ra tin g te m p e ra tu re s and n o t c a ta ly s t d iffe r e n c e s .
I t a p p e a rs t h a t no d e s u lfu r iz a tio n o r d e n itro g e n iz a tio n is ta k in g
p la c e .
T h is co u ld be because th e liq u e fa c tio n re a c tio n is ta k in g place
a t th e o u te r s u rfa c e o f th e coal p a r tic le and th e p r o d u c t b e in g an a lyze d
is f o r th e m ost u n re a cte d co a l.
I t can also be seen t h a t th e b u lk o f
th e c o n v e rs io n is in th e oil f r a c t io n .
I t has also been show n th a t as th e p e rc e n ta g e o f c a ta ly s t in th e
coal in c re a s e s fro m 1 .5 to 6 p e rc e n t m etal on coal, th e y ie ld o f a s p h a l­
te n e s decrea ses s ig n if ic a n tly and th e m o le cu la r w e ig h t o f th e a s p h a l­
te n e and hexa n e s o lu b le o il decrease [4 5 ].
E.
T h e E ffe c ts o f H y d ro g e n C h lo rid e on Coal C o n v e rs io n
Each o f th e c a ta ly s ts d is c u s s e d in th e p re v io u s s e c tio n w ere ru n
a g a in , th is tim e u s in g a 5 p e rc e n t m ix tu re o f h y d ro g e n c h lo rid e in
h y d ro g e n as th e c a r r ie r g a s.
T h e p ro d u c ts w e re aga in an a lyze d f o r
coal c o n v e rs io n and p r o d u c t n itro g e n and s u lf u r c o n te n t.
T h e re s u lts
61
o f th e s e ru n s a re show n in T a b le X .
T a b le X l shows th e h y d ro g e n
c h lo rid e c a ta ly z e d c o n v e rs io n b ro k e n dow n in to th e in d iv id u a l fr a c tio n s .
As can be se e n , in each case, th e a d d itio n o f 5 p e rc e n t HCI to th e
fe e d gas re s u lts in a s ig n ific a n t in c re a s e in to ta l c o n v e rs io n .
T h is data
is c o n s is te n t w ith p re v io u s b a tc h coal h y d ro g e n a tio n s tu d ie s [8 , 3 7 ].
T h is da ta a p p e a rs to fo llo w th e coal liq u e fa c tio n m echanism p ro po sed b y
W eller [4 4 ].
T h e th e rm a l s p lit t in g o f th e coal a p p a r e n tly is c a ta ly z e d
b y th e halogen a c id , and th e s e e ith e r p o ly m e riz e to fo rm u ris o lu b le p r o ­
d u c ts o r a re s ta b iliz e d b y th e a d d itio n o f h y d ro g e n a tio n to fo rm s o lu b le
\
p r o d u c ts .
T h e h y d ro g e n a tio n a p p e a rs to be c a ta ly z e d b y th e m etal.
T h e in c re a s e in c o n v e rs io n h e re is s ig n ific a n t.
t le d iffe r e n c e is seen f o r th e v a rio u s c a ta ly s ts .
H o w e v e r, v e r y l i t ­
T h is c o u ld be due to
th e HCI c a ta ly z e d re a c tio n b e in g th e ra te lim itin g s te p .
Note th a t even
th e n o n - c a ta ly tic coal was in c re a s e d s ig n ific a n tly d ue to th e a d d itio n o f
HCI alo n e .
B y c o m p a rin g da ta in T a b le IX and X I , i t is n o te d th a t m ost
o f th e in c re a s e in c o n v e rs io n comes in th e m ost d e s ira b le o il f r a c t io n .
T a b le X l l p re s e n ts th e n itr o g e n and s u lf u r c o n te n ts o f th e p r o ­
d u c ts o f r u n s p e rfo rm e d w ith h y d ro g e n c h lo rid e .
A g a in no d e su lfu riza ^-
tio n o r d e n itro g e n a tlo n a p p e a rs to have ta k e n pla ce .
A g a in , i t is
p la u s ib le t h a t th e analyzed, p r o d u c t is f o r th e m ost p a r t u n re a cte d c o a l,
in d ic a tin g th a t th e re a c tio n o c c u rs on th e o u te r coal surfa ce,.
62
T a b le X .
T h e E ffe c t o f H y d ro g e n C h lo rid e on Coal C o n v e rs io n
C a ta ly s t
T o ta l C o n v e rs io n H0
C oC I2
1 0.8
4 4 .2
S n C I2
17.2
38.3
C u C I2
.1 6 .5
3 7 .8
N iC I2
15.5
3 7 .6
Z n C I2
24 .2
3 4 .3
FeCI2
8 .3
3 4 .2
4 .2
2 5 .0
N o n -c a ta ly tic
T a b le X I .
T o ta l C o n v e rs io n .H0-H C I
.
T h e E ffe c t o f H y d ro g e n C h lo rid e On In d iv id u a l Coal
C o n v e rs io n
C o n v e rs io n
C a ta ly s t
O il
A s p h a lte n e
A s p h a lto l
T o ta l
C oC I2
29 .7
12 .6
1 .9
44.2
S n C I2
33.3
4.1
0 .9
38.3
C u C I2
33 .2
3 .7
0 .9 .
37.8
N iC I2
3 4 .2
2 .9
0 .5
37 .6
Z n C I2
31 .9
2 .4
0 .0
34.3
FeCI2
29 .9
4 .3
0 .0
3 4.2
N o n -C a ta ly tic
20 .6
3 .5
0 .9
25.0
63
Table X I I .
F.
Nitrogen and S ulfur in HCI Runs
C a ta ly s t
% S u lfu r
% N itro g e n
C oC i2
0 .6 7
1 .3 4
S n C I2
0.5 3
0 .9 7
C u C I2
0.3 6
0L98
N iC I2
0.5 2
1.0 0
Z n C I2
0.3 9
1 .0 4
FeCI2
0.5 6
1.0 3
No n - c a ta ly tic
0.2 9
----
U n re a c te d coal
0 .5 7
1.0 3
T h e E ffe c t o f T e m p e ra tu re on Coal C o n v e rs io n
A s show n b y F ig u re 14, th e coal, c o n v e rs io n in c re a s e d r a p id ly
w ith in c re a s in g te m p e ra tu re .
T e m p e ra tu re s used w e re 600, 500, and
4000C u s in g h y d ro g e n as th e c a r r y in g gas arid n ic k e l c h lo rid e ca ta ­
ly z e d co a l.
T h is can be e x p la in e d b y th e p o s tu la te d m echanism o f coal h y d r o ­
g e n a tio n
[4 4 ].
Coal is s p lit th e rm a lly to fo rm re a c tiv e fra g m e n ts .
I t is p la u s ib le t h a t a t lo w e r te m p e ra tu re s , th e r e is in s u ff ic ie n t t h e r ­
mal e n e rg y to s p lit th e coal th u s p ro d u c in g less m o le c u la r fra g m e n ts .
T h is th e n w o u ld re d u c e th e n u m b e r o f a c tiv e s ite s a v a ila b le f o r
64
A - Oi l Conversion
O - T otal Co n ve r si o n , Oi l
Asph a lt en e , Asphaltol q
T emperature , °C
Figure 14.
The Effect of Tem perature on Coal Conversion.
65
s ta b iliz a tio n in to s o lu b le p ro d u c ts b y th e a d d itio n o f h y d ro g e n .
T h is
t r e n d is s u p p o rte d b y da ta f r e q u e n t ly re p o rte d in th e c u r r e n t coal
liq u e fa c tio n lite r a t u r e
[7 , 8, 2 2 ].
Wood and W iser r e p o r t 700°C is
re q u ire d to a ch ie ve 65 p e rc e n t c o n v e rs io n , w h ile B ie g a lk e re p o rts n o n c a ta ly tic c o n v e rs io n to be o v e r 30 p e rc e n t a t 6 0 0 °C .
G.
T h e E ffe c t of. C a r r ie r Gas Flow Rate on Coal C o n v e rs io n
A s show n b y F ig u re 15, th e coal c o n v e rs io n decrea ses w ith
in c re a s in g c a r r ie r gas flo w ra te .
T h e c a r r ie r gas used in th is in v e s ti­
g a tio n was h y d r o g e n , w h ile n ic k e l c h lo rid e c a ta ly tic coal was used .
H y d ro g e n flo w ra te s te s te d w e re 9, 14, and 30 s ta n d a rd c u b ic fe e t p e r
h o u r.
T h is tr e n d w o u ld be e x p e c te d sin ce an in c re a s e in h y d ro g e n
flo w r a te , o r lin e a r v e lo c ity th ro u g h th e tu b e , also w o u ld re d u c e th e
coal re s id e n c e tim e .in th e re a c tio n zo n e .
T h is tr e n d is also re p o rte d
b y Wood and W iser u s in g s im ila r e q u ip m e n t [2 2 ].
T h e y also r e p o r t a
coal p a r tic le re s id e n c e tim e o f tw o to s ix seconds f o r a o n e -h a lf in ch
re a c to r tu b e w h ic h com pares w ith a gas re s id e n c e tim e o f 0 .8 seconds
f o r th e same s itu a tio n .
T h is seems to in d ic a te th a t coal s tic k s to th e
h o t tu b e w all to some e x te n t.
T h e gas re s id e n c e tim e f o r th e v a rio u s flo w ra te s a re p re s e n t in
T a b le X I I I , based on s ix fe e t o f heated re a c to r le n g th .
66
A -O
il
Conversion
O - T otal Co nv er si on , Oi l
Asphal tene , Asphaltol
Ca r r i e r Gas F low,
Figure 15.
scfh
The Effect of C a rrie r Gas Flowrate on Coal Conversion.
67
Table X I I I .
Reactor Gas Residence Time
R esidence Tim e
H y d ro g e n Flow Rate
For S ix FOot R e a c to r, Sec.
( s c fh )
H.
9
0 .1 9
14
0.12
30
0 .0 6
T h e E ffe c t o f P re s s u re on Coal C o n v e rs io n
T h e e ffe c t o f p re s s u re on coal c o n v e rs io n is show n on F ig u re 16.
As n o te d , th e c o n v e rs io n d ro p s s h a r p ly w ith d e c re a s in g p re s s u re s .
P re s s u re s te s te d w e re 1 ,0 0 0 , 800, and 500 p s ig .
N ic k e l c h lo rid e c a ta ­
ly t ic coal was used w ith h y d ro g e n as th e c a r r ie r g a s .
T h is tre n d is
also v e r ifie d f r e q u e n t ly in th e lite r a t u r e and is p la u s ib le sin ce th e use
o f in c re a s e d p re s s u re in te n s ifie s th e a v a ila b ility o f h y d ro g e n to re a c t
w ith fra g m e n te d m olecules [7 , 22, 23, 2 8 ].
68
A - Oi l Conversion
O - Total Con v e r s i o n , Oi l
Asph a lt en e , Asphaltol
Pressure ,
Figure 16.
psig
The Effect of Pressure on Coal Conversion.
69
I.
S u lf u r and N itro g e n ' C o n te n t o f O il and A s p h a lte n e F ra c tio n s
T o f u r t h e r c h a ra c te riz e a n y d e h itro g e n a tio n a n d /o r d e s u lfu r iz a ­
tio n w h ic h to o k place d u r in g th e re a c tio n , s u lf u r and n itro g e n c o n te n t
o f th e o il and a s p h a lte n e p r o d u c t o f se le cte d ru n s w e re d e te rm in e d .
S ince th e o il and a s p h a lte n e fr a c tio n s w e re e x tra c te d in to a s o lv e n t,
th e y w e re f u r t h e r is o la te d to be a n a ly z e d .
T h is was done b y b o ilin g
o f f th e s o lv e n t u n t il a w e ig h t ra tio o f a b o u t th re e p a r ts s o lv e n t to one
p a r t o il o r a s p h a lte n e re m a in e d .
lyze d f o r s u lf u r and n itr o g e n .
T h u s , t h is is th e sam ple t h a t was a n a ­
T h e re s u lts a re show n in T a b le X I V .
I t can be n o te d t h a t th e a p p e a ra n ce o f d e s u lfu r iz a tio n and d e n itro g e n a tio n o f th e oil and a s p h a lte n e p ro d u c ts p r o b a b ly o c c u rs .
Note th a t th e
da ta re p o rte d re p re s e n ts th e n itro g e n and s u lf u r o f th r e e to one ra tio
o f s o lv e n t to p r o d u c t and th e v o lu m e tric means o f d e r iv in g th is sample
was a p p ro x im a te .
70
T a b le X I V .
S u lf u r and N itro g e n C o n te n t o f Oil and A s p h a lte n e
F ra c tio n s
F ra c tio n
S u lf u r
N itro g e n
G14 O il
0 .0 9
0.011
G15 O il
0.075
0.016
G l6 O il
0.1 6
0.008
G14 A s p h a lte n e
0.1 0
0.012
G15 A s p h a lte n e
0 .1 4
0.009
G16 A s p h a lte n e
0 .07
0.011
G17 A s p h a lte n e
0 .1 5
0.012
Hf
CO N C LU SIO N S
T h e fo llo w in g c o n c lu s io n s can be made:
(1 )
P u lv e riz e d coal is a d i f f ic u l t medium to feed u n ifo r m ily and
r e p r o d u c ib ly a t h ig h p re s s u re s (2 )
U n re a c te d coal c o n ta in s 0 .4 p e rc e n t o ils , 0 .2 p e rc e n t a s p h a l­
te n e s , and 0.1 p e rc e n t a s p h a lto ls f o r a to ta l c o n v e rs io n o f 0 .7 p e rc e n t.
(3 )
T h e coal fe e d ra te is a fu n c tio n o f c a r r ie r gas flo w ra te u n d e r
th e o p e ra tin g c o n d itio n s used in th is th e s is w o rk .
(4 )
C o n v e rs io n o f coal in to c h a ra c te riz a b le liq u id p ro d u c ts can be
made u s in g ra p id coal liq u e fa c tio n m e th o d s.
(5 )
Im p re g n a te d m etal c h lo rid e c a ta ly tic coal y ie ld s h ig h e r c o n ­
v e rs io n s u n d e r s im ila r d p e ra tin g c o n d itio n s th a n n o n - c a ta ly tic coal.
(6 )
T h e a d d itio n o f h y d ro g e n c h lo rid e to th e c a r r ie r gas h y d r o ­
gen strea m r e s u lts in a s ig n ific a n tly h ig h e r c o n v e rs io n f o r b o th metal
c h lo rid e c a ta ly z e d and n o n -c a ta ly z e d coal.
(7 )
T h e n itro g e n and s u lf u r c o n te n t o f th e s o lid p r o d u c t ana­
lyze d rem ain v ir t u a ll y u n ch a n g e d fro m u n re a cte d c o a l.
(8 )
In cre a se s in te m p e ra tu re in c re a s e th e coal c o n v e rs io n
a tta in e d w ith c a ta ly tic coal.
(9 )
In cre a se s in c a r r ie r gas flo w ra te decrease th e coal c o n v e r­
sion a tta in e d w ith c a ta ly tic coal.
72
(1 0 )
In cre a se s in system p re s s u re in cre a se th e coal c o n v e rs io n
a tta in e d w ith c a ta ly tic coal.
(1 1 )
D e n itro g e n a tio n and d e s u lfu r iz a tio n a re e v id e n t in th e oil
and a s p h a lte n e fr a c tio n s o f th e liq u id p ro d u c ts .
RECO M M ENDATIO NS FOR FU TUR E S T U D Y
Due to th e o p e ra tin g pro b le m s e n c o u n te re d w ith th e p re s e n t
e x p e rim e n ta l a p p a ra tu s in th is th e s is w o r k , . s e ve ra l m a jo r m o d ific a ­
tio n s a re s u g g e s te d b e fo re a tte m p ts a re u n d e rta k e n to o b ta in a n y
m ore e x p e rim e n ta l d a ta .
O p e ra tin g p ro b le m s such as coal fe e d e r p lu g ­
g in g , e x tre m e te m p e ra tu re v a r ia tio n s , and re a c to r p lu g g in g re s u lte d
in th e m a kin g o f 2 .5 tim es as m any e x p e rim e n ta l ru n s as re p o rte d
h e re in .
E q u ip m e n t ch a n g e s t h a t a re recom m ended a re :
(1 )
In s ta ll a h y d ro g e n ( c a r r ie r g a s ) p re -h e a tin g s y s te m .
In
v ir t u a lly all s im ila r re s e a rc h w h ic h is p r e s e n tly b e in g c o n ­
d u c te d a ro u n d th e c o u n tr y , a h y d ro g e n p r e - h e a tin g system
is u s e d .
T h is co u ld be done b y b u ild in g a h e a tin g system
s im ila r to th e one p r e s e n tly used to h e a t th e r e a c to r.
A
le n g th o f co ile d tu b in g w ra p p e d a ro u n d an in te r n a lly heated
steel p ip e lo cate d d ir e c t ly u p s tre a m o f th e h y d ro g e n in le t o f
th e coal fe e d e r w o u ld seem to do th e jo b .
C a re sh o u ld be
e x e rc is e d to in s u re th a t th e p re - h e a t system h e a t in p u t is
s ig n if ic a n tly o v e rd e s ig n e d so la rg e h ea t t r a n s f e r ra te s d ue to
chan ges in la rg e flo w ra te s do n o t a ffe c t th e re a c to r te m p e ra ­
tu re .
(2 )
In s ta ll a p r o d u c t q u e n ch s y s te m .
A g a in , c u r r e n t re se a rch
in d ic a te s t h a t a q u e n c h in g system be used to m inim ize th e
74
tim e th e p ro d u c ts o f coal liq u e fa c tio n a re e xpo sed to h ig h
te m p e ra tu re s .
T h is q u e n ch co u ld be done b y in je c tin g a cold
flo w o f h y d ro g e n o r n itro g e n in to th e re a c to r system ju s t
d o w n stre a m fro m th e re a c to r o u tle t.
B a th in g th e p ro d u c t
c o lle c tio n vessel in w ater, w o u ld n o t be a s u ita b le m ethod o f
q u e n c h sin ce th e m a n u fa c tu re r o f th a t piece o f e q u ip m e n t
in d ic a te s t h a t loss o f s t r u c t u r a l in t e g r it y m ay o c c u r in th a t
s itu a tio n .
(3 )
In s ta ll la r g e r d ia m e te r re a c to r tu b in g .
T h e use o f la rg e r
d ia m e te r tu b in g w o u ld h e lp b o th th e h e a t t r a n s f e r problem
e n c o u n te re d and also te n d to re d u c e th e pro b le m s e n co u n ­
te re d w ith re a c tio n p lu g g in g .
I t is recom m ended th a t th e
o u ts id e d ia m e te r be a m inim um o f 5 /1 6 " w ith 3 /8 " tu b in g
d e s ir e d .
(4 )
In s ta ll a p r o d u c t c o n d e n s in g s y ste m .
T h is th e s is w o rk has
d e te rm in e d t h a t a p r o d u c t c o n d e n s in g system is im p e ra tiv e i f
f u t u r e w o rk is to g e n e ra te m ore m e a n in g fu l d a ta .
I t is
b e lie v e d t h a t p r e s e n tly m uch o f th e liq u id p r o d u c t is p a ssin g
th r o u g h th e p r o d u c t c o lle c tio n vessel as a v a p o r.
E vidence
o f t h is is th e f a c t th a t a t a r r y liq u id s u b s ta n c e can be
fo u n d in s id e th e pro ce ss lin e s and p re s s u re r e g u la to r d o w n ­
strea m fro m th e c o lle c tio n v e s s e l.
A d d itio n a l e vid e n c e is th e
fo rm a tio n o f an o ily la y e r in th e e x it gas s c r u b b e r .
I t is
75
recom m ended t h a t a second p r o d u c t c o lle c tio n vessel be
added to th e flo w system m ounted below a v e r tic a l w a te r
c o n d e n s e r.
New e x p e rim e n ts t h a t a re recom m ended in c lu d e :
(1 )
C h a ra c te riz a tio n o f cond ensed liq u id p ro d u c ts b y c o n v e rs io n
m ethods and s u lf u r and n itro g e n m ethods o u tlin e d h e r e in .
(2 )
A n a ly s is o f e x it gas stream b y gas c h ro m a to g ra p h y .
T h is
w o u ld p r o b a b ly r e q u ir e th e use o f a p re s s u riz e d flo w m eter
u p s tre a m o f th e re a c to r to m easure c a r r ie r gas flo w ra te s .
Gas
c h ro m a to g ra p h y m ethods a re re p o rte d b y o th e r in s titu tio n s
p e rfo rm in g s im ila r re s e a rc h .
(3 )
T e s t th e e ffe c t o f a h y d ro c a rb o n v e h ic le on p r o d u c t c o n v e r­
s io n .
V e h ic le s su ch as p ro p y le n e , pen ete ch o i l , d e c a lih e ,
to lu e n e , and t e tr a lin e co u ld s e rv e as a h y d ro g e n d o n o r and
ha ve been show n to be e ffe c tiv e in s im ila r p re v io u s ba tch
s tu d ie s .
(4 )
Exam ine th e r e c o v e r a b ility o f th e c a ta ly s t used so th e c a ta ­
ly s t econom ics can be s tu d ie d ,
(5 )
C h a ra c te riz e liq u id p ro d u c ts b y ASTM d is tilla tio n s .
Longer
ru n tim es may be needed to g e n e ra te a d e q u a te am ounts o f
p r o d u c t.
76
(6 )
Run with o t h e r ha lo gen s in t h e ga s feed s u c h as boron t r i ­
f l u o r i d e a nd h y d r o g e n fl o u r i d e .
(7)
Run u s i n g solid SRC r a t h e r t h a n coal f o r t h e fee d m a te ri a l.
(8 )
Determine t h e e f f e c t of c a t a l y s t c o n c e n t r a t i o n on coal c o n v e r ­
sions a nd p r o c e s s economics.
(9 )
Determine t h e e f f e c t of HCI c o n c e n t r a t i o n in t h e feed g a s on
coal c o n v e r s i o n , p r o d u c t d e n i t r o g e n a t i o n , / a n d p r o c e s s
economics.
(10)
Determine t h e e f f e c t of h i g h e r p r e s s u r e s on coal c o n v e r s i o n .
APPENDIX
78
Ta bl e XV.
Typi cal Run Data
__________
RUN F-6
Run Con dition s
Temperature
SOO0C
Pressure
1,000 pslg
Flowrate
30 scfh
Feeder Setting
10
Coal Feed
C o p p e r C a t a l y z e d , -60 mesh,
d r ie d
C a r r i e r Gas
H2
Ba ro m et er
639.3
Ambient Tem perature
73°F
Time
Flowrate
Temperature
(M in .)
(Sec/rev)
(°C)
Remarks
0
7 .4
480
Start
5
8.4/7.7
500
OK
11
8 .0
510
21
8.3/7.8
490
29
8.1
510
38
8 .0
500
46
8.1
490
53
8 .2
500
60
8 .0
510
60 m i n .
8 .0 A v g .
499 A v g .
Flowrate
=
360
8. 0
x
492
760
x
639.3:
534
Backoff Heat
Sh utd ow n
= 35 s cfh
T a b le XVI.
R e s u lts of P relim in ary R ese arch
Run
A v g . Run
Run
A y g . Run
A v g . Product
No.
Temp.
Pressure
Gas Flowrate
Collection Rate
(°c)
(psig)
(scfh)
El
470
1,000
40
68
13.1
0.6
0.3
E2
450
1,000
38
68
9 .0
2.1
0.8
ES
455
800
39
67
5.8
0.1
0.1
E4
460
1,000
26
19
6.7
0 .4
0.1
ES
470
500
39
60
2.1
0. 5
0.1
Oil
C on ver sio n %
A s p h a lt e n e
Asphaltol
(g/hr)
TABLE XVi I.
Run No.
Fl
F2
F3
F6
F7
Fll
G6
G7
G8
G9
GlO
G12
Gl 4
G15
Gl 6
G17
G18
Gl 9
G20
G21
Final Run D ata, O p e r a t i n g P a ra m e te r s
A v g . Run
Temperature
(°C)
'
480
501
508
499
491
486
494
504
515
505
503
491
498
491
416
508
500
593
495
501
Run
Pressure
(psig)
Avg.. Run
Gas Flowrate
(scfh)
C a r r i e r Gas
1,000
1,000
1,000
1,000
1,000
1,000
1,000
35
37
37
35
Ho
HpHCI
HpHCl
35
1 ,0 0 0
30
1,000
1,000
1,000
1,000
1,000
30
HpHCI
H2
Ho
HpHCI
HpHCI
30
30
HpHCI
1 ,0 0 0
1,000
1,000
1,000
1,000
800
500
36
36
.30
30
30
30
9
14
30
30
30
h|
h|
Hp
HxHCI
Hf
Ho
Hp
Ho
Hp
Hp
4
Product
Collection Rate
(g/hr)
30
20
7
3
3
3
51
15
10
34
33
29
35
22
15
6
16
22
27
15
C a t a ly s t
None
None
CuCIp
CuCIp
CoCIp
ZnCIp
FeCIp
FeCIp
ZnCIp
CoCIp
SnCIx
SnC U co
NiCIp2 0
NiCU
NiCU
NiCU
NiCU
NiCU
NiCU
NiCI^
T a b le XVI I I ,
Final Run D ata, C o n v e rsio n s
Run No.
Oil
Fl
F2
F3
F6
F7
Fll
G6
G7
G8
G9. .
GIO
G12
Gl 4
G15
Gl 6
G17
Gl 8
G19
G20
G21
3 .8
20.6
33.2
13.0
29.7
16.9
5 .7
29.9
31.9
9 .9
33.3
14.3
34.2
14.0
7 .5
16.4
19.1
25.6
4 .3
1.3
C on v er si o n %
Asphaltene
0 .3
3 .5
3.7
2 .8
12.6
6.1
1.9
4 .3
2.4
0 .9
4.1
2 .9
2 .9
1.5
1.3
1.8
4 .9
5.1
0 .8
0.4
Asphaltol
Total
% Sulfur
% Nitrogen
0.1
0.9
0 .9
0.7
1.9
1 .0
0.7
0 .0
4 .2
25.0
37.816.5
44.2
24.0
8 .3
34.2
34.3
10.8
38.3
17.2
37.6
15.5
9 .2
18.7
24.8
31.3
5 .3
1 .1
0.79
0.29
0.36
0.57
0. 67
0. 54
0.61
0.56
0.39
0.51
0.53
0.55
0.52
0.62
0.62
0.54
1.10
0.0
0 .0
0 .9
0.0
0 .5
0.0
0.4
0 .5
0.8
0.6
0 .2
0.0
\
— —
0.98
-
— —
0.97
1.10
1.00
1.14
1.08
“
— —
—
0. 64
--
-
1.34
1.13
1.00
1.03
1.02
.
1.26
0.86
1.00
1.16
LITERATURE CITED
83
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Waterman, John Jay
C o n tin u o u s s h o r t r e s i ele n c e tim e c o a l l i q u e ­
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