Professional Documents
Culture Documents
OP
ACETYLENE PROM METHANE
H.J. LEON
ABSTRACT
The p y r o l y s i s o f methane d i l u t e d w i t h n i t r o g e n at
1200C and 1.00
atm t o t a l p r e s s u r e was
r e a c t o r made o f alundum.
i n v e s t i g a t e d i n a flow
The r e a c t i o n i s u n a f f e c t e d by a
The
governed
i n i t i a l r a t e of decomposition o f methane i s
by
_ 5.7
3P0H4
dt
(atm/sec)
P0CH4
f o r p a r t i a l p r e s s u r e s r a n g i n g from 0.100
t o O.672
atm.
atm,
atm,
a c e t y l e n e up t o 0.010
atm, hydrogen up to
following equations:
PCH =
P0CR4
PC H
2
e" 4.80
- 2
~
f P0CH4
P0CH4)
-4.80(l+p CH ) t
o
f i - -3-50(l+2PoCH ) t l
e
(1 +
11
5 f o
15$
7%
An a u t o c a t a l y t i c e f f e c t o f a c e t y l e n e , r e p r e s e n t e d
by the e m p i r i c a l
equation
dPC2Hp
,
= (0.00586)(32.3)
d t
was observed
PCH
f
+ [32.3
*i
- 4.80(l+PoCH4)|PC H2
Ill
In
the
presenting
this thesis
r e q u i r e m e n t s f o r an
of
British
it
freely available
agree that
for
Columbia,
Department o r
advanced degree at
that
copying or
gain
shall
not
his
s h a l l make
for reference
and
study.
of
be
granted
by
representative.
the
Chemical
July
29,
1958
my
for financial
written
Engineering
Columbia,
Head o f
thesis
I t i s understood
of t h i s t h e s i s
a l l o w e d w i t h o u t my
The U n i v e r s i t y o f B r i t i s h
V a n c o u v e r $, C a n a d a .
Date
further
Humberto
Department
University
Library
publication
be
the
of
the
p u r p o s e s may
by
fulfilment
I agree that
permission
scholarly
in partial
permission.
Leon
ACKNOWLEDGEMENT
I am indebted
t o Dr. D.S. S c o t t
f o r h i s guidance i n t h i s r e s e a r c h , and
to the S h e l l
for financial
March 17,
1958
Columbia
Canada
Dear S i r :
I submit h e r e w i t h my
thesis, Kinetics of
P r o d u c t i o n o f A c e t y l e n e from Methane, i n q u a d r u p l i c a t e ,
i n p a r t i a l f u l f i l m e n t o f the requirements f o r the
degree o f Master of A p p l i e d Science i n Chemical
E n g i n e e r i n g , at the U n i v e r s i t y o f B r i t i s h
Columbia.
Respectfully yours,
Humberto Leon
CONTENTS
Acknowledgement
Abstract
II
Diagrams
Introduction
Apparatus
Procedure
11
A n a l y t i c a l Methods
13
Homogeneity o f the R e a c t i o n
15
Effect
19
o f barbon D e p o s i t i o n
E f f e c t of the P a r t i a l Pressures o f
Methane and Acetylene
23
Limitations
37
Cone l u s ions
40
Bibliography
41
Appendix
42
IV
DIAGRAMS
c o n v e r s i o n of methane versus
the s u r f a c e - t o - v o l u m e - r a t i o
3 Percentage
18
c o n v e r s i o n o f methane versus
r e a c t i o n time c o r r e c t e d f o r carbon
d e p o s i t i o n a t v a r i o u s on-stream-times..... 22
4 The p a r t i a l p r e s s u r e of methane versus
r e a c t i o n time at v a r i o u s i n i t i a l
partial
27
pressures of methane
5 The p a r t i a l pressure of a c e t y l e n e v e r s u s
r e a c t i o n time a t v a r i o u s I n i t i a l methane
p a r t i a l pressures
28
6. The p a r t i a l p r e s s u r e o f a c e t y l e n e
versus
the p a r t i a l p r e s s u r e o f methane a t
33
constant r e a c t i o n time
7
methane
38
p a r t i a l pressures
KINETICS OF PRODUCTION
OF ACETYLENE FROM METHANE
Introduction
o f methane d i l u t e d w i t h n i t r o g e n , a t
done on
Using a
carbon,
From t h e . r e s u l t s o f h i s exper-
an energy o f a c t i v a t i o n o f 79 k-cal/mole
and a
f i r s t order r e a c t i o n r a t e constant
(1)
k 1.0 x 1 0
The r a t e equation.was
1 2
e -79585/RI
reaction
A l s o i n 1932, H.H. S t o r c h
his
r e p o r t e d the r e s u l t s o f
Although
(2)
+ H2
CH
CH
+ CH
C H
(4)
C H ^=T C H
2
+ H
(5)
Cg^,
C H
+ H
(k , r )
(6)
C H ^=^
+ H
(k , r )
(3)
CH
2C
(k
l f
r )
x
(k , r )
2
(k , r )
3
(7)-
fc*Q-
d t
r r r\ rfaJ-+ r, r x
3
k,60+
r, ( t y
kj k k,(H J+ k J ^ k / c H J
4
reaction
rate
T h i s r a t e e q u a t i o n accounted f o r the
r e a c t i o n due t o the i n c r e a s e
The
i n hydrogen
concentration.
r o l e o f f r e e r a d i c a l s i n the decomposition o f
on a carbon f i l a m e n t
using
tellurium
mirrors.
(heterogeneous r e a c t i o n ) , methylene
f o r the homogeneous
reaction.
4
Rice and coworkers
CH
or o f the homogeneous
CH
CH
+ H
Z=t CH
+ H
reactions
(9)
(10)
reaction
CH
CH
2 CH
g
A.S. Gordon
Consequently, the
ethane, e t h y l e n e
phenanthrene,
A c a t a l y t i c e f f e c t o f a c e t y l e n e on the
decomposi-
i n 1949,
decomposiu s i n g an
10""-' mm Hg.
r a d i c a l s a t 1000C.
In the
On the
radicals
The i n c r e a s i n g demand f o r a c e t y l e n e , b o t h as w e l d i n g
The a c e t y l e n e produced by
purification
partial
The e l e c t r i c a l d i s c h a r g e
In the p a r t i a l o x i d a t i o n o r S a c h s s e ^ p r o c e s s , the
heat r e q u i r e d f o r the decomposition r e a c t i o n i s s u p p l i e d by
the combustion o f p a r t o f the hydrocarbons w i t h pure oxygen.
The gases are preheated s e p a r a t e l y , and then f e d to a burner,
"
In the thermal
c r a c k i n g o r Wulff
11
x
p r o c e s s , the
sec, and c o o l e d
immediately.
T h i s o p e r a t i o n i s best c a r r i e d out i n a r e g e n e r a t i v e
furnace,
a make c y c l e .
a c e t y l e n e from hydro-
high
y i e l d s o f a c e t y l e n e may be o b t a i n e d .
Although many f a c t s are known about the decomposit i o n o f methane, the mechanism o f the r e a c t i o n i s not y e t
f u l l y understood.
In the present
to o b t a i n i n f o r m a t i o n which, added t o t h a t a l r e a d y e x i s t i n g ,
might h e l p c l a r i f y the chemical k i n e t i c s of the r e a c t i o n , w i t h
a s p e c i a l r e g a r d to the p r o d u c t i o n o f a c e t y l e n e .
Apparatus
The
study-
The
995$
nitrogen
flows c o u l d be
reducers and
needle
The p u r i f i c a t i o n c h a i n c o n s i s t e d of bubblers
contain-
The
g l a s s t u b i n g 1.0 mm
of
cm l o n g , and were
The p r e s s u r e
drop
f l a s k and
o f the c a p i l l a r i e s , measured a t
c a l i b r a t e d a g a i n s t a P r e c i s i o n Wet
as F v s . ( P
hour, P
the
.Ap),
i s the mean a b s o l u t e p r e s s u r e
i n i n . Hg,
the p r e s s u r e
were allowed
to mix
"Ascarite" for f i n a l
i n a f l a s k whose o u t l e t tube
drying.
and Ap
The
is
gases
contained
Precision
figure
Wet
I.
Test
Meter
Schematic
Acetylene
Flow
Diagram
Abaorption
of
Continuous
System.
Sampler
Exhaust
The
A rubber s e a l a t the
s e a l a t the o u t l e t s i d e h e l d the
thermocouple t u b i n g i n p l a c e .
at 5 . 0 cm^.
The two l / l 6 - i n c h h o l e s
i n the thermo-
The
of 9 5 $ magnesia.
The
r e a c t i o n products
passed through a s e t t l i n g
o f the t a r ,
m a t e r i a l balances.
i n the
o f the gases
combined w i t h t h e t i m e
of
the gases.
a tube
which
A f t e r b e i n g measured, t h e gases
filled
with
flow
rate
flowed,through
o f carbon
dioxide
i n t e r f e r e s w i t h t h e a c e t y l e n e d e t e r m i n a t i o n . The a c e t -
y l e n e was a b s o r b e d
silver
o f t h e r u n , gave t h e o u t l e t
nitrate
i na fritted
solution.
A l t e r n a t i v e l y , w h i l e the adjustments
silica
c o n t a i n i n g water
object
instead
of silver nitrate
t o the r e a c t i o n
the runproper.
water
o f t h e dummy s y s t e m was t o p r o d u c e
as p o s s i b l e
ing
g e l instead
ejector.
tube
solution.
as l i t t l e
The
alteration
c o n d i t i o n s a t t h e moment o f s t a r t -
The g a s e s were t h e n e x h a u s t e d
through a
A sample o f t h e r e a c t i o n p r o d u c t s a f t e r a c e t -
y l e n e a b s o r p t i o n c o u l d be drawn by a c o n t i n o u s s a m p l i n g d e v i c e
made w i t h two t w o - l i t e r
oxygen, hydrogen,
Burrel-type
flasks.
This
sample was a n a l y z e d f o r
c a r b o n m o n o x i d e , methane, a n d n i t r o g e n
gas a n a l y s i s s e t .
The
current
f o r t h e c a r b o r u n d u m h e a t e r was s u p p l i e d
by a D.G. g e n e r a t o r o f a d j u s t a b l e
voltage.
The t h e r m o c o u p l e
was
made o f p l a t i n u m - p l a t i n u m 1 3 $ r h o d i u m
was
r e c o r d e d b y a "Speedomax" r e c o r d e r a n d c o n t r o l l e r ,
o n - o f f controlL.on t h e h e a t i n g c u r r e n t ,
The
temperature
period of less
ten
In a
minutes,
and t h e temperature
acting
o s c i l l a t e d w i t h an amplitude
t h a n one m i n u t e .
the effect
with
through a r e l a y .
o f 4C and a
Since each r u n l a s t e d
about
o f t h e o s c i l l a t i o n s was a v e r a g e d o u t
The a c t i o n o f
o f the p r e s s u r e o s c i l l a t i o n was
2 mm Hg.
Procedure
With the system open t o the atmosphere a t the c a p i l l a r y downstream p r e s s u r e manometer, the r e a c t o r was s l o w l y
brought up t o temperature.
While
the r e a c t o r was b e i n g
was r e g u l a t e d
the s u c t i o n
p r e s s u r e ; the n i t r o g e n
The me-
After
f o r the product gases t o d i s p l a c e the gases between the r e a c t o r and the a c e t y l e n e a b s o r p t i o n system, and t o approach
e q u i l i b r i u m between the product gases and the water i n the
Wet Test Meter, and then the gases were switched from the
dummy system t o the a c e t y l e n e a b s o r p t i o n system, the i n i t i a l
time and volume recorded, and the gas sampling
The
r a t e o f sampling
device opened.
c o u l d be r e g u l a t e d by a p i n c h cock i n
The p r e s s u r e o f the
during
switched
back t o the dummy system and the f i n a l volume and time r e corded.
t o atmospheric
p r e s s u r e the
T h i s method avoided
After
be
the
turned
carbon
line
and
the
silver nitrate
(upstream
solution
sample was
side
first
was
was
bubbler
filtered
diluted
and
silver acetylide,
the u n r e a c t e d
0.16
(about
acetylene, tests
with a i r .
mg-mole) were
The
below.
out.
the
from
solution),
F i n a l l y the
the
silver
outlet
Methods
i n the r e a c t i o n
by b u b b l i n g
the
N silver nitrate
N),
gas
e f f i c i e n c y of the
In every
and
was
deter-
through
solution
and t i -
thyocianate
a c c o r d i n g t o the V o l h a r d method.
were c a r r i e d
w i t h water at 25C
appear
could
disconnected
s i l v e r against potassium
diluted
was
t i t r a t e d , and
acetylene produced
solution
the heat
analyzed.
The
trating
and
to a v o i d l o s i n g
Analytical
m i n e d as
suction
s i l v e r acetylide
nitrate
gas
burned, the
off.
The
the
was
out u s i n g c o m m e r c i a l
test
1 atm
absorption
2 0 0 ml
of
acetylene
of acetylene
t o t a l pressure
saturated
(approximately
used.
results
of the
acetylene
absorption
In
tests
7.9
Table 1.
Run
Plow Rate
Bubbler
(mole/hr)
Element
plate
cold
7.17
10
plate
cold
3.83
io
plate-*
cold
4.03
Solution
Acetylene
(mg-mole)
hot
7.50
cylinder
hot
7.20
cylinder
hot
7.10
cylinder
Table 1.
acetylene
a b s o r p t i o n would be o b t a i n e d u s i n g a c y l i n d r i c a l bubbler
a hot s i l v e r n i t r a t e s o l u t i o n .
the a c e t y l e n e was
absorbed
and
of
at 6 mole/hr,
Cylindrical
The
solution
experiments.
s o l u b i l i t y of a c e t y l e n e i n water c o n s t i t u t e s
T h i s e r r o r c o u l d be
beginning
T e s t Meter i s a c e t y l e n e
However, because o f
a b s o r p t i o n was
o u t l e t gas
analyzed
the e r r o r was
condi-
considered
disregarded.
sample c o l l e c t e d a f t e r
acetylene
i n a B u r e l l - t y p e gas a n a l y s i s s e t
Test Meter
The
i n thd Wet
determined by a b s o r p t i o n i n potassium
s o l u t i o n , oxygen by a b s o r p t i o n In a l k a l i n e , p y r o g a l l o l
cupric,oxide,
c a t a l y s t , and n i t r o g e n by
difference.
D e t a i l s about the d e t e r m i n a t i o n
y i e l d o f the r e a c t i o n and
"Sample Run"
i n the
o f the
acetylene
Appendix.
Homogeneity o f the
Reaction
v a r i e d from 3 . 6 to 24.6
cm" ,
1
maintaining
T h i s means t h a t the i n i t i a l p a r t i a l
reac-
pressure
o f methane was
a l s o kept constant
accom-
Results
R a t i o Runs" o f the
Appendix.
atm,
Table 2.
Run
o f 1200C and a r e a c t o r
appear below.
E f f e c t of Surface-to-Volume
s/v
Conversion
P0CH4
Time
(cm- )
(atm)
(sec)
3.6
0.322
0.0249
11.1
13.1
0.328
0.0248
11.7
20.6
0.328
0.0251
13.2
24.6
0.326
0.0246
14.5
Ratio
of
CH4
{%)
D i s c u s s i o n of
Results
The
r e s u l t s recorded
i n Table
2 show the
effect
and
to carbon, f o r an i n i t i a l methane
of
The
and a r e a c t i o n
p l o t o f t o t a l methane
on
i n the
surface-to-volume r a t i o i n c r e a s e d the r a t e of r e a c t i o n by
only 30%,
t h e r e f o r e , i t i s concluded t h a t the r e a c t i o n
l a r g e l y homogeneous.
due
to one
The
was
i n c r e a s e i n r a t e observed may
be
of the f i r s t
or second sup-
position.
a) The
r e a c t i o n i s c a t a l y z e d by the alundum
s u r f a c e to a v e r y . s l i g h t e x t e n t .
b) The
r e a c t i o n i s c a t a l y z e d by the alundum
s u r f a c e to a l a r g e r extent
of f r e e alundum s u r f a c e i s decreased by
i n the r e a c t o r .
the amount
carbon d e p o s i t i o n
of
and,
2.
on
18
tO
IS
20
conversion of methane
ratio
2S
(cm' )
1
versus the
is controlling, i.e.
tempera-
the s u r f a c e area a v a i l a b l e
temp-
The
s l i g h t l y i n c r e a s e d temp-
conversion.
d) Heat t r a n s f e r to the p e l l e t s i s c o n t r o l l i n g ,
i . e . , there i s a temperature g r a d i e n t between the r e a c t o r
w a l l and
i s l o c a t e d and,
consequently,
c o n v e r s i o n would correspond
E f f e c t of Carbon
Deposition
The
reac-
20
reac-
Results
T a b l e 3 shows t h e r e s u l t s
out t o determine
the e f f e c t
was
carried
but
f o r a 24.6 c m
out under c o n d i t i o n s
Table
Run
cm
- 1
surface-to-volume
ratio.
Average
on-stream
time ( s e c )
386
similar
surface-to-volume
- 1
3.
Effect
s/v
carried
o f c a r b o n d e p o s i t i o n a t 1200G
and
o f the t e s t s
o f r u n 6 which
t o t h o s e o f r u n 3,
ratio.
o f Carbon D e p o s i t i o n
PC H2
(atm)
(atm)
(atm)
CH
13.1
0.278
0.071
0.00240
11.7
1.53
cm"
PH
% conversion
PCH4
C H
2
1576
13.1
0.284
0.062
0.00217
10.2
1.37
2654
13.1
0.290
0.057
0.00185
9.4
1.16
10
3654
13.1
0.292
0.051
8.8
2600
24.6
0.292
0.059
0.00182
9.3
1.13
Discussion of Results
The
figures
shown i n T a b l e 3 i n d i c a t e
that the
percentage
c o n v e r s i o n o f methane t o a c e t y l e n e and t h e t o t a l
percentage
c o n v e r s i o n o f methane d e c r e a s e w i t h t h e o n - s t r e a m
t i m e and c o n s e q u e n t l y , w i t h t h e amount o f c a r b o n d e p o s i t e d
in
the r e a c t o r .
version
I t was t h o u g h t
that
this
c o u l d be e x p l a i n e d by t h e d e c r e a s e
decrease
i n con-
i n reaction
time w h i c h
sition
accompanied
t h e volume r e d u c t i o n b y c a r b o n
i n the r e a c t o r .
possibility
An a t t e m p t
was made t o v e r i f y
a t any o n - s t r e a m - t i m e ,
c o n v e r s i o n o f methane t o c a r b o n a n d h y d r o g e n .
o f 2 . 0 0 mole/hr
flow rate
o f 2 . 0 g/cm
F o r t h e meth-
a n d a n assumed c a r b o n
density
1
(ID
where
this
b y e s t i m a t i n g t h e volume o f t h e c a r b o n d e p o s i t e d
in the reactor
ane
depo-
/ t
30,000
jo
(cm^) i s t h e volume o f c a r b o n d e p o s i t e d i n t h e
r e a c t o r , X ^ , {%) i s t h e c o n v e r s i o n o f methane t o c a r b o n , a n d
t ''",(sec) i s t h e o n - s t r e a m
osited
time.
The v o l u m e s o f c a r b o n
i n t h e r e a c t o r were d e t e r m i n e d b y g r a p h i c a l
t i o n on a p l o t
o f XQ v s . t
, and appear
w i t h the r e a c t o r volumes c o r r e c t e d
and
the corrected
variation
r e a c t i o n time
corrected
T a b l e 4
integra-
on T a b l e 4 t o g e t h e r
f o r carbon d e p o s i t i o n V '
r
r e a c t i o n times t * .
o f the percentage
dep-
F i g u r e 3 shows t h e
c o n v e r s i o n o f methane w i t h t h e
f o r carbon
Corrections
deposition.
t o R e a c t o r Volume a n d
R e a c t i o n Time f o r C a r b o n D e p o s i t i o n
Run
t'
CH
(cm5)
(cm3)
(sec)
{%)
0.14
4.86
0.0242
11.7
0.53
4.47
0.0224
10.2
0.80
4.20
0.0210
9.4
10 ^ 1.07
3.93
0.0197;
8.8
22
Figure J .
Percentage
conversion
time corrected
on-stream times
of methane
for carbon
versus
deposition
at
reaction
various
It
which
i s apparent
cannot
accompanies
that
be a c c o u n t e d
a rapid
decrease
i n conversion
f o r b y a change i n r e a c t o r volume
t h e d i s a p p e a r a n c e o f t h e alundum s u r f a c e .
t h e s u r f a c e becomes
covered w i t h carbon
e n t i r e l y homogeneous
and t h e p o i n t s
the r e a c t i o n
l i e on a smooth
As
becomes
line
through the o r i g i n .
The
homogeneity o f the r e a c t i o n
v e s s e l was
r e p o r t e d by K a s s e l
comparison
o f the r e s u l t s
were c a r r i e d
13*1
cm"
virtually
The
ference
o f r u n s 6 and 9 ( T a b l e 3 ) ,
and a t on-stream
a l l t h e alundum s u r f a c e was
results
are p r a c t i c a l l y
i n surface-to-volume
Effect
coated
and c a n be s u p p o r t e d by a
out a t s u r f a c e - t o - v o l u m e r a t i o s
respectively,
i n a carbon
which
o f 24.6 and
time
such
covered w i t h
t h e same i n s p i t e
that
carbon.
o f the d i f -
ratio.
o f the P a r t i a l
Pressures
o f Methane a n d A c e t y l e n e
In o r d e r t o i n v e s t i g a t e
pressures
tion
the e f f e c t
of the p a r t i a l
o f methane a n d a c e t y l e n e o n t h e r a t e
o f methane and t h e r a t e
of
decomposi-
o f f o r m a t i o n o f a c e t y l e n e , the
p a r t i a l p r e s s u r e s o f a c e t y l e n e , methane, and h y d r o g e n
were
determined
partial
a t v a r i o u s r e a c t i o n times
p r e s s u r e s o f methane.
for five
initial
The
r e a c t i o n temperature,
s u r e , and t h e s u r f a c e - t o - v o l u m e
all
these
runs, while
was v a r i e d b y c h a n g i n g
in
the f e e d .
by
changing
tor
volume
the r e a c t o r t o t a l
r a t i o were k e p t
the i n i t i a l
pres-
constant f o r
methane p a r t i a l
pressure
t h e p r o p o r t i o n o f methane t o n i t r o g e n
The v a r i a t i o n
the t o t a l m o l a l
i n r e a c t i o n time
was
obtained
f e e d r a t e and k e e p i n g
the reac-
constant.
Results
The
tests
f o r the d e t e r m i n a t i o n
the p a r t i a l p r e s s u r e s
of
decomposition
o f methane and a c e t y l e n e
o f 13.1 cm" .
1
ious r e a c t i o n times
Discussion
atm, a n d a s u r f a c e - t o -
The r e s u l t s
obtained
methane p a r t i a l
f o r the v a r pressures
5.
of Results
carried
d i f f i c u l t y was
encountered
o u t a t t h e h i g h e r methane p a r t i a l
b e c a u s e o f t h e l a r g e amount
reactor
o f 1.00
and i n i t i a l
Considerable
tests
on t h e r a t e
out a t a r e a c t i o n temperature o f
1200C, a r e a c t o r p r e s s u r e
a p p e a r on T a b l e
of
o f methane and t h e r a t e o f f o r m a t i o n o f
a c e t y l e n e were c a r r i e d
volume r a t i o
o f the e f f e c t
o f carbon
and i n t h e r e a c t o r o u t l e t .
methane p a r t i a l
pressure
e d f o r a r e a c t i o n time
deposited
Thus,
f o r an
i n the
pressures
i n the
initial
o f 0.672 atm t h e f l o w r a t e
o f 0.03
s e c c o u l d n o t be
requir-
maintained
Table 5 .
Run
E f f e c t o f I n i t i a l Methane P a r t i a l
Pressure
P0CH4
Time
PCH4
PC2H2
PR"2
(atm)
(sec)
(atm)
(atm)
(atm)
21
0.100
0.0322<
0.089
0.0.0089
0.019
22
0.100
0.0536
0.081
0.00159
0.034
16
0.221
0.0260
0.187
0.00148
0.050
18
0.221
0.0321y
0.186
0.00192
0.054
17
0.221
0.0465 r
0.172
0.00280
0.077
0.336
0.0248
0.278
0.00240
0.071
19
0.336
0.0314/
0.280
0.00312
0.081
11
0.336
0.0452 *
0.250
0.00502
0.107
12
0.485
0.0241
0.405
0.00294
0.118
20
0.485
0.032l/
0.385
0.00410
0.124
13
0.485
0.0470 *
0.346
0.00707
0.177
- 15
0.672
0.0490 *
0.435
0.00957
0.271
26
for a sufficient
l e n g t h o f time t o c o l l e c t a r e l i a b l e
sample.
(0.221,
(O.672,
0.100
atm).
The i n i t i a l r a t e o f
f o r the v a r i o u s
initial
order r e a c t i o n r a t e constants
(k ) calculated f o r
Q
Table 6 .
I n i t i a l R e a c t i o n Rates
P0CH4
-d(P0H )/dt
(atm)
(atm sec-1)
*o
Relative
(sec" )
1
Weight
0.100
O.35
3.5
0.221
1.12
5-1
0.336
2.00
5-9
0.485
3-08
6.4
0.672
4.87
7.2
to i n d i c a t e an i n i t i a l r e a c t i o n o f
27
0.0/
0.02
Reactfon
Figure
4.
The partial
pressure
various
initial
methane
O.OJ
Time
of methane
partial
0.04
O.OS
(szc)
versus
reaction
pressures
time
at
Figure 5. The
partial
pressure
of acetylene
pressures
2-9
the f i r s t
order.
A s s i g n i n g a r b i t r a r y weights to the
as i n d i c a t e d i n Table 6,
5.7
see -
constants
would be
c a l c u l a t e d from K a s s e l ' s e q u a t i o n
The
experimental
p l o t t e d as l o g (PCH^)
v s
sec"!
(1).
'
data on methane p a r t i a l
pressures
by
the
equation
(12)
= 4.80
( 1 + P0CH4
seer
correl-
by
P0H
(13)
= PoCH
.-><
1+
P o C H
4 >*
values
formula.
determined
pressure
f o r v a r i o u s constant a c e t y l e n e p a r t i a l pressures.
Table
7*
Rate o f Change o f A c e t y l e n e
Partial
PC2H2
(atm/sec)
(atm)
(atm)
0.100
0.221
0.336
Rate
0.033
O.O63
0.104
PCH4
0.087
0.200
0.314
Rate
0.034
O.O65
CH
0.074
0.001
P0CH4
Pressure
0.485
0.672
0.106
0.131
0.162
0.182
0.299
0.425
0.592
Rate
0.067
0.115
0.141
0.171
PCH4
O.I64
0.280
0.404
0.562
Rate
0.130
0.151
0.186
PCH4
0.265
0.387
0.534
Rate
0.153
0.190
0.203
PCH4
0.252
0.368
0.512
Rate
0.173
0.214
0.226
PCH4
0.240
0.358
0.492
Rate
0.227
0.238
PCH4
0.346
0.472
0.002
P
0.003
0.004
0.005
0.006
0.007
31
A p l o t o f the r a t e o f change o f the a c e t y l e n e p a r t i a l pressure v s . the methane p a r t i a l pressure
shows s t r a i g h t
S i m i l a r l y , a p l o t o f the r a t e of change
partial
PC2H2
(14)
k2
PCH
PC2H2
= 0.23
sec"
(16)
sec"
21
R e p l a c i n g the p a r t i a l p r e s s u r e o f methane by i t s
e q u i v a l e n t i n terms o f time, d e f i n e d by Eq.
r a t e equation
the a c e t y l e n e
f o r the a c e t y l e n e p a r t i a l
(17)
(13),
pressure
Po
k]_
expression
CH
( 6 * 3 * - a**!*)
k^
satisfactorily.
data
Searching f o r a b e t t e r c o r r e l a t i o n ,
p a r t i a l p r e s s u r e was p l o t t e d
sure a t constant
Figure
a g a i n s t t h e methane p a r t i a l
reaction times.
6, y i e l d e d
straight
ing a relationship
the acetylene
pres-
The p l o t , w h i c h a p p e a r s i n
lines
through
the o r i g i n ,
suggest-
o f the form
(18)
PC H
2
i n which F ( t ) , the r a t i o
= nt)
PCH
of acetylene p a r t i a l pressure to
methane p a r t i a l p r e s s u r e , c o u l d be r e p r e s e n t e d b y
(19)
F ( t ) = 0.00586
A comparison o f the v a l u e s
and
those
(e52-3 * - i )
o f F ( t ) determined
c a l c u l a t e d f r o m E q . (19)
Table
Reaction
8.
Acetylene
Time
from F i g u r e 6
c a n be s e e n
t o Methane
i n Table
Ratio
Experimental
Calculated
F(t)
F(t)
0.00
0.0000
0.0000
0.01
0.0025
0.0022
0.02
0.0057
0.0053
0.03
,0.0096
0.0096
0.04
0.0154
0.0151
0.05
0.0236
0.0236
(sec)
8.
S u b s t i t u t i o n o f E q . (19) i n E q . (18) g i v e s f o r t h e
acetylene p a r t i a l
pressure
33
0.10
0.20
OJO
Methane
Figure
6.
The partial
pressure
pressure
of methane
0.40
0.S0
Partial
of acetylene
ot constant
0.60
Pressure
versus
reotion
the
time
(otm)
partial
(20)
or,
(21)
PC H2
0.00586 ( e ^ '
2
t _
P0CH4
rearranging,
PC H2
2
Eq.
0.00586 Po C H 4
(21)
,(32.3 - k i ) t _
-kit
0.00586 t a k i n g the p l a c e o f
/(kT_
with
i n F i g u r e 5
(22)
dpQ^jjjj
= (0.00586)(32.3) P C H 4 + (32.3 - kx)
PC H
2
i s a constant, whereas
partial
pressure.
curves, o n l y k
(or the c o e f f i c i e n t o f
the dependence o f
with
were c a r r i e d
out,
pressure
o f the a c e t y l e n e par-
effect
o f a c e t y l e n e on the r e a c t i o n r a t e .
by K a s s e l ,
( E q . 2 3 ) , the r a t e o f f o r m a t i o n o f a c e t y l e n e
d(C H )
2
(23)
VC2H.4> -r (C H )(H )
4
+ r
5(H2)
-k (C H )
5
12
as has been shown by Watt
of E q . ( 2 2 )
The p o s i t i v e term
(32.3-k )PC H
1
experiments,
o f acetylene i s n e g l i g i b l e with
t r a t i o n can be s e t equal t o z e r o .
these experiments
Although the r e s u l t s o f
i n v a l i d a t e the assumption
o f the n e g l i g i b l e
r a t e of f o r m a t i o n o f a c e t y l e n e , they do not n e c e s s a r i l y c o n t r a d i c t the proposed mechanism, which cannot be t e s t e d f o r r e p r e s e n t a t i o n o f the a c e t y l e n e r a t e o f f o r m a t i o n without knowing
the r e a c t i o n r a t e constants k^, k^, and k^ o f Eq. ( 4 ) ,
and
(5),
(6) r e s p e c t i v e l y .
13
Laidler
main o v e r a l l r e a c t i o n s a r e :
(24)
2 GH ^ ^ G H
4
(25)
CH
that
+ 3 H
+ 2H
show t h a t the
dp
dt
d(CH )
dt
4
d(C H )
- 2
dt
2
d(C H )
dt
2
arecarbon,
1 2 7
OCHA-
PCHA
1 ? P O C H *
Substitution
Eq.(25).
the pressure-time
curves.
However,
(2S)
PH =
*
\ ! . e- '
[
5
1 + POCH^
2 P 0 C H
*]
)
Eq.(28).
Limitations
The experiments
These
38
0.01
0.0 J
0,02
0.04
Reaction
Figure
7. The partial
pressure
at various initio/
of hydrogen
methane
partial
0.05
Time (sec)
versus
reaction
pressures
time
c o n d i t i o n s were the f o l l o w i n g :
1)
con-
2)
of methane was
Although i t was
u n a f f e c t e d by a carbon s u r f a c e and
c a t a l y z e d by an alundum s u r f a c e , no e f f o r t was
slightly
made to com-
during
a run.
3)
4)
The s m a l l q u a n t i t i e s of t a r d e p o s i t e d
i n the
i n the
calculations.
5)
E r r o r s i n the a c e t y l e n e
d e t e r m i n a t i o n due to
Test Meter or i n s u f f i c i e n t
i n t o account.
6)
and
i n the gas
all
times.
The
Test
Meter,
Conclusions
be
following
1200C:
1)
The
2)
The
r e a c t i o n i s s l i g h t l y c a t a l y z e d by an
The
initial
surface.
dum
surface.
3)
an.
alun-
r e a c t i o n i s of f i r s t
p r e s s u r e s o f methane from 0 . 1 0 0 t o O . 6 7 2
4)
on the
Acetylene has
reaction.
order w i t h
for partial
atm.
an apparent a u t o c a t a l y t i c e f f e c t
BIBLIOGRAPHY
(1934).
J . Am. Chem. S o c ,
(1939).
87 (1935).
13.
(1950).
APPENDIX
Sample Run
.
, #7
Run,,
Barometric
Room Temperature
1952
29.7
Pressure
i n . Hg
22.5C
. 1200C
R e a c t i o n Temperature
Reactor Pressure
J u l y 16,
Surface-to-Volume R a t i o
29.9
i n . Hg (0.2
i n . Hg. ,gauge)
13.1,cm~
1
. CH
. N
Downstream Pressure
H 2 0).
(in.
6.00
7.90
Hg)
. (g-mole/hr)
32.0
. .
32.0.
measurements:
1.000
Temperature
76P = 535R
Pressure
Time
f t
( P H 2 0 . = 0.9
(27.2)(1.000) _
(21.85X535)
621 sec
1.96
3.92
Volume
Moles
Plow Rate
"
i n . Hg)
i n . Hg
"
o n 9
-00232-lb-nole
L056
g-mole
43
Rate
Acetylene
= 6.12 g-Mole/hr
>
yield:
S t a r t w i t h 1 0 0 ml o f 0 . 7 0 4 N s i l v e r n i t r a t e
A f t e r removal o f the s i l v e r a c e t y l i d e
solution.
p r e c i p i t a t e , the s o l u t i o n
(100)(0.704)
= 70.4 mg-mole
( 1 0 ) ( 3 8 . 3 ) ( O . I 6 4 ) = 6 2 . 8 mg-mole
Acetylene
absorbed
( 7 0 . 4 - 6 2 . 8 ) / 3 = 2.53 mg-mole
Acetylene
concentration
( 2 . 5 3 ) / ( 1 . 0 5 6 ) ( 1 0 0 0 ) = 0.240 mole %
Orsat Gas A n a l y s i s
Operation
Initial
(1) 100.0
KOH
(2) 100.0
Pyrogallol
(3)
99.8
CuO tube
(4)
92.8
KOH.
(5)
92.5
Reduce t o
(5 r )
50.2,
Add 0
(6'j
96.9
(6) 178.5
(7') 67-7
(7) 124.7
Catalyst
(8),
tube
KOH
(8)
52.9
(8)
97.3
Pyrogallol
(9') 38.0
(9)
70.0
Figures
(7'),
B u r e t t e Reading
( 6 ) , ( 7 ) , (8),
(9)
are r e s p e c t i v e l y ( 6 ' ) ,
( 9 ' ) m u l t i p l i e d by ( 9 2 . 5 / 5 0 . 2 ) .
Component
co
Calculation
2
H
2
CO
CH
N
Sample
mole %
O u t l e t Gas
mole %
g-mole/hr
(l)-(2)
0.0
(2)-(3)
0.2
(3)-(4)
7.0
7.1
0.43
(4)-(5)
(6)-(8)
3
(5)-(CH )
0.3
0.3
0.02
#27.7-'
27-8
1.70
#64.8
64.6
3-96
0.240
100.0
Total
100.0
0.0147
6.12
(2.0)(27.1)
(92.5)
Q m 6
'
t 3 ^
C + 2 H
C H
Methane converted t o a c e t y l e n e
2
= 0.195 g-mole/hr
I n l e t flow r a t e o f methane
1.70
g-mole/hr
calibration.
(6.12
Average flow r a t e
Run
No.
Reactor diameter
(cm)
1.11
R a t i o Runs
1.11
1.11
1.11
Reactor l e n g t h (cm)
5.2
7-5
9.4
9.4
T o t a l r e a c t o r volume (cm3)
5.0
7.3
9.1
9.1
0.353
0.353
100
:.180
250
Volume o f p e l l e t s (cm3)
0.0
2.3
4.1
4.1
Free r e a c t o r volume
5-0
5.0
5.0
5.0
18.1
26.2
32.7
32.7
(cm )
0.0
39-1
70.5
90.3
Reactor s u r f a c e (cm )
18.1
65.3
103.2
123.0
20.6
24.6
P e l l e t diameter
(cm)
No. o f p e l l e t s
(cm^)
I n t e r n a l r e a c t o r area
Area of p e l l e t s
S/V R a t i o (cm" )
1
# Not s p h e r i c a l
(cm )
2
3.6
13.1
K-