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KINETICS OP PRODUCTION

OP
ACETYLENE PROM METHANE

H.J. LEON

A THESIS SUBMITTED IN PARTIAL FULFILMENT OF


THE REQUIREMENTS FOR THE DEGREE OF
MASTER OF APPLIED SCIENCE
IN CHEMICAL ENGINEERING

We accept t h i s t h e s i s as conforming t o the


standard r e q u i r e d

from candidates f o r the

degree o f MASTER OF APPLIED SCIENCE.

Members o f the Department o f

THE UNIVERSITY OF BRITISH COLUMBIA


March 1 9 5 8

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

carbon s u r f a c e but s l i g h t l y c a t a l y z e d by an alundum s u r f a c e .

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.

The experimental pressure-time curves f o r methane


up t o 0.70
0.30

atm,

atm,

a c e t y l e n e up t o 0.010

and time up t o 0.05

atm, hydrogen up to

sec were reproduced by the

following equations:
PCH =

P0CR4

PC H
2

e" 4.80

= 0.00586 (e32.3 t _].) p


PH2

- 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

i n the i n i t i a l stages o f the r e a c t i o n .

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

for extensive copying of t h i s

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

Caribbean Petroleum Company


assistance.

March 17,

1958

Dean o f the F a c u l t y o f A p p l i e d Science


U n i v e r s i t y of B r i t i s h
Vancouver, B. C ,

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

1. Schematic flow diagram o f system


2. The percentage

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

The p a r t i a l p r e s s u r e o f hydrogen versus


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
38

p a r t i a l pressures

KINETICS OF PRODUCTION
OF ACETYLENE FROM METHANE

Introduction

The o b j e c t o f t h i s i n v e s t i g a t i o n was t o study the


thermal.decomposition

o f methane d i l u t e d w i t h n i t r o g e n , a t

1200C and a t o t a l p r e s s u r e of 1.00

atm w i t h the Idea o f

determining the dependence o f the r e a c t i o n r a t e on-the r e a c t o r


s u r f a c e and on the p a r t i a l p r e s s u r e s o f methane, a c e t y l e n e ,
and hydrogen.

The f i r s t k i n e t i c work o f any importance

done on

t h i s s u b j e c t was r e p o r t e d i n 1932 by L.S. K a s s e l .

Using a

s t a t i c system made o f q u a r t z , sometimes coated w i t h

carbon,

K a s s e l a r r i v e d a t the c o n c l u s i o n t h a t the i n i t i a l p a r t o f the


r e a c t i o n was f i r s t order and homogeneous, apart from an induct i o n p e r i o d o f obscure n a t u r e .
iments made a t temperatures
determined

From t h e . r e s u l t s o f h i s exper-

between 976 and 1113C, K a s s e l

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

determined from the i n i t i a l

reaction

rates at various i n i t i a l reaction pressures.


p

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

experiments on the decomposition of methane by a carbon

f i l a m e n t i n a bulb immersed i n l i q u i d n i t r o g e n o r oxygen.


He found the e a r l y products o f the r e a c t i o n t o be ethane and
unsaturates corresponding t o the e t h y l e n e f o r m u l a .

Although

he found an average energy o f a c t i v a t i o n o f 77 k-cal/mole, i n


agreement w i t h the value obtained by K a s s e l , h i s i n d i v i d u a l
v a l u e s ranged from 40 t o 120 k-cal/mole, and h i s temperatures
may have been i n e r r o r .
Based on Storch's a n a l y s i s o f the products o f the
r e a c t i o n , on the r e s u l t s o f h i s own experiments, and on
t h e o r e t i c a l c o n s i d e r a t i o n s , K a s s e l suggested the f o l l o w i n g
mechanism f o r the homogeneous decomposition o f methane:

(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

from which the f o l l o w i n g r a t e e q u a t i o n may be deduced

(7)-

fc*Q-

d t

2 [k,k k,k k,fcH.f - r, i\r,, r+r* CHJ4")


a

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

where k and r stand f o r the forward and r e v e r s e


constants r e s p e c t i v e l y .
initial first

reaction

rate

T h i s r a t e e q u a t i o n accounted f o r the

order r e a c t i o n r a t e f o r the methane decomposi-

t i o n and, although not q u a n t i t a t i v e l y , f o r the r e t a r d a t i o n o f


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

methane and other hydrocarbons has been i n v e s t i g a t e d by


B e l c h e t z and R i d e a l ^ , and R i c e ^ ,
They a r r i v e d at the c o n c l u s i o n
place

on a carbon f i l a m e n t

using

tellurium

mirrors.

t h a t , when the r e a c t i o n takes

(heterogeneous r e a c t i o n ) , methylene

r a d i c a l s are p r e s e n t i n s t e a d o f the methyl r a d i c a l s i n the


mechanism proposed by K a s s e l

f o r the homogeneous

reaction.

4
Rice and coworkers

had found methyl r a d i c a l s , but these were

p r o b a b l y the r e s u l t o f the secondary


(8)

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

i n 1948, working a t temperatures b e t -

ween 1000 and 1100C w i t h a r e a c t o r made o f p o r c e l a i n ,

i n v e s t i g a t e d the decomposition o f methane i n the presence o f


steam and i n the presence o f n i t r o g e n .

He found that steam

r e a c t e d w i t h carbonaceous m a t e r i a l formed i n the decomposition


o f methane and not -with methane d i r e c t l y .

Consequently, the

decomposition o f methane was u n a f f e c t e d by d i l u t i o n w i t h steam


or n i t r o g e n .

Gordon used a mass spectrograph t o analyze the

product, gases, among which he found hydrogen,

ethane, e t h y l e n e

a c e t y l e n e , and, In s m a l l q u a n t i t i e s , propylene, p r o p y l i n e , and


benzene.

In the carbonaceous m a t e r i a l produced i n the r e a c -

t i o n were i d e n t i f i e d : naphthalene, anthracene,


and pyrene.

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-

t i o n o f methane and a l a r g e i n i t i a l e f f e c t caused by the


p o r c e l a i n s u r f a c e on the r e a c t i o n are r e p o r t e d .

The r o l e o f f r e e r a d i c a l s on the methane


7
t i o n was s t u d i e d a g a i n by A.J.B. Robertson

i n 1949,

decomposiu s i n g an

incandescent p l a t i n u m f i l a m e n t and p r e s s u r e s o f the order o f

10""-' mm Hg.

The mass spectrometer used f o r the a n a l y s i s

showed methyl but no methylene

r a d i c a l s a t 1000C.

In the

dehydrogenation o f ethane t o ethylene at 950C, he found no


methyl o r e t h y l r a d i c a l s and the r e a c t i o n proceeded a t the
same r a t e In the presence o f methyl r a d i c a l s from methane.
He concluded t h a t the decomposition o f methane on a p l a t i n u m
f i l a m e n t took p l a c e by m o l e c u l a r dehydrogenation.
other hand, Rice and H e r z f e l d

On the

have proposed, on the b a s i s o f

experimental r e s u l t s , a sound mechanism f o r the homogeneous


decomposition o f ethane, w i t h the p a r t i c i p a t i o n o f f r e e

radicals

Apart from i t s importance i n the f i e l d o f Chemical


K i n e t i c s , the decomposition of methane has importance i n i n d u s t r y , In the manufacture o f hydrogen and carbon b l a c k from n a t u r a l gas.

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

f u e l and as a s t a r t i n g m a t e r i a l f o r organic s y n t h e s i s , has l e d


to i n v e s t i g a t i o n s i n t o the p o s s i b i l i t y o f manufacturing a c e t y l e n e , i n commercial s c a l e , from methane and o t h e r l i g h t hydrocarbons contained i n n a t u r a l gas.

The a c e t y l e n e produced by

decomposition o f l i g h t hydrocarbons and subsequent

purification

i s cheaper but s l i g h t l y more impure than the a c e t y l e n e produced


by the c a r b i d e p r o c e s s , which accounts f o r most o f the a c e t y l ene p r e s e n t l y i n u s e .

Three g e n e r a l methods are i n use at p r e s e n t f o r


decomposing the hydrocarbons: e l e c t r i c a l d i s c h a r g e ,
o x i d a t i o n , and thermal c r a c k i n g .

partial

The e l e c t r i c a l d i s c h a r g e

method developed by Schoch^ at the U n i v e r s i t y o f Texas, uses


a r a p i d l y r o t a t i n g blower to stream a sheet o f gas between the
electrodes.

Y i e l d s o f 21% u s i n g a methane feed, and a c e t y l e n e

c o n c e n t r a t i o n s i n the e f f l u e n t gas o f n e a r l y 1 0 $ , are r e p o r t e d .

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,

where the r e a c t i o n takes p l a c e at 100C.

The gases are

quenched by a water spray a f t e r a r e s i d e n c e time o f 0 . 1 s e c .


Y i e l d s o f a c e t y l e n e may be as h i g h as 30$.

"
In the thermal

c r a c k i n g o r Wulff

11
x

p r o c e s s , the

hydrocarbons, d i l u t e d w i t h steam o r i n e r t gases, are q u i c k l y


heated
allowed

t o the c r a c k i n g temperature o f more than 1000C,


to r e a c t f o r about 0.05

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,

i n which the r e f r a c t o r y m a t e r i a l " a b s o r b s heat o f combustion


d u r i n g a heat

c y c l e , and surrenders i t t o the r e a c t a n t s d u r i n g

a make c y c l e .

These methods o f producing

a c e t y l e n e from hydro-

carbons are based on the f a c t that a c e t y l e n e i s formed i n the


i n i t i a l stages o f the r e a c t i o n , so t h a t b y . a r r e s t i n g the
decomposition

a f t e r a short contact time, reasonably

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

study, an e f f o r t was made

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

A diagram o f the apparatus used i n t h i s


appears i n F i g u r e 1.

The

gases were i n commercial c y l i n d e r s

of 9 9 $ methane from the Matheson Company and


from the Canadian L i q u i d A i r Company.
a d j u s t e d by a combination o f p r e s s u r e
valves.

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-

i n g a l k a l i n e p y r o g a l l o l s o l u t i o n f o r the removal o f oxygen


and carbon d i o x i d e , and d r y i n g tubes c o n t a i n i n g s i l i c a g e l
f o r the n i t r o g e n and

The

" D r i e r i t e " f o r the methane.

c a p i l l a r y flow meters were made from p i e c e s


i n diameter and 7*6

g l a s s t u b i n g 1.0 mm

immersed i n a water b a t h kept a t 20C.

of

cm l o n g , and were
The p r e s s u r e

drop

a c r o s s the c a p i l l a r i e s , i n d i c a t e d by water manometers, and


the downstream p r e s s u r e
mixing

f l a s k and

o f the c a p i l l a r i e s , measured a t

i n d i c a t e d by a mercury manometer, were

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),

Test Meter, and c o r r e l a t e d

vtfiere F Is the flow r a t e i n gram moles per

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

drop across the c a p i l l a r y i n i n . Hg.

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

r e a c t o r was made o f an alundum tube o f 7/16 i n .

i n s i d e diameter, 11/16 i n . o u t s i d e diameter and 30 i n . l o n g .


Two s e c t i o n s o f alundum thermocouple t u b i n g o f 3 / 8 i n . o u t s i d e
diameter, l / l 6 i n . double bore, and 18 I n . l o n g were f i t t e d
i n s i d e the alundum tube l e a v i n g i n the c e n t e r a space f o r the
r e a c t i o n chamber, whose l e n g t h c o u l d be a d j u s t e d by the s l i d i n g
i n and out o f the thermocouple t u b i n g .
i n l e t end and an asbestos

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 .

The r e a c t o r was packed w i t h

alundum p e l l e t s o f v a r i o u s s i z e s , but i t s f r e e volume was kept


constant
couple

at 5 . 0 cm^.

The two l / l 6 - i n c h h o l e s

i n the thermo-

tubing a t one s i d e c a r r i e d the thermocouple wires and

a l s o served as gas i n l e t to the r e a c t i o n chamber, whereas the


h o l e s a t the other s i d e served as r e a c t o r o u t l e t .

The

r e a c t o r was p l a c e d Inside a t u b u l a r carborundum

heater o f 1-1/8 i n . i n s i d e diameter, 2-1/8 i n . o u t s i d e diameter


and

28 i n . long, i n s u l a t e d w i t h 6 i n . "Superex" and 2 i n .

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

f l a s k f i l l e d w i t h g l a s s wool, where carbon and t a r were c o l l e c ted.


and

No e f f o r t was made to determine the nature

o f the t a r ,

s i n c e the amount was s m a l l , i t was n o t c o n s i d e r e d

m a t e r i a l balances.

i n the

The volume of gases produced was measured

by a P r e c i s i o n Wet Test Meter.

The volume r e a d i n g from the

meter, the temperature, and the average p r e s s u r e

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

" A s c a r i t e " f o r the removal

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.

glass bubbler containing 10$

A l t e r n a t i v e l y , w h i l e the adjustments

were b e i n g made, t h e g a s e s were d e t o u r e d t h r o u g h a dummy


containing

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 " A s c a r i t e " a n d a dummy b u b b l e r

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

by the continous sampling d e v i c e and the d e t e r m i n a t i o n o f


t o t a l acetylene.

The p r e s s u r e i n the r e a c t i o n zone was measured


through a t a p i n the i n l e t rubber s e a l o f the r e a c t o r by a
mercury manometer which had on-off c o n t r o l on a b l e e d e r o f
the s u c t i o n l i n e o p e r a t i n g through a r e l a y .

The a c t i o n o f

the c o n t r o l l e r c o u l d be a d j u s t e d by the stopcock i n the b l e e d e r


line.

The maximum amplitude

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

heated the c a p i l l a r y water bath temperature

was r e g u l a t e d

at 20C, the s i l v e r n i t r a t e bubbler was f i l l e d w i t h 100 ml o f


s o l u t i o n o f known c o n c e n t r a t i o n (about 0.7 N) and the gas
sample f l a s k was i n s t a l l e d and f r e e d o f a i r .

Once the r e a c t o r was up t o temperature,


was

the s u c t i o n

turned on w i t h the dummy system i n o p e r a t i o n and thus,

a i r c i r c u l a t e d through the r e a c t o r t o burn any carbon deposits present.

The pressure c o n t r o l l e r was s e t a t 760mm Hg,

i . e . , a h e i g h t o f mercury equal t o the d i f f e r e n c e between one


atmosphere and the a c t u a l atmospheric

p r e s s u r e ; the n i t r o g e n

was turned on and the a i r i n l e t was s l o w l y c l o s e d .

The me-

thane was then turned on and the flows were a d j u s t e d t o the


d e s i r e d r a t e s a c c o r d i n g tbo the c a l i b r a t i o n curves.
steady c o n d i t i o n s were reached,

After

s u f f i c i e n t time was allowed

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 water l i n e between the two f l a s k s .

The p r e s s u r e o f the

gas a t the Wet Test Meter was recorded about f o u r times


each r u n and averaged

during

f o r the c a l c u l a t i o n o f the gas volume.

To complete the run, the gas sample was i s o l a t e d


and the pressure o f the gas made s l i g h t l y p o s i t i v e t o a v o i d
contamination w i t h a i r ; the r e a c t i o n products were

switched

back t o the dummy system and the f i n a l volume and time r e corded.

The methane was turned o f f , the stop cock i n the

b l e e d e r o f the s u c t i o n l i n e was shut and when the c a p i l l a r y


downstream p r e s s u r e decreased

t o atmospheric

system was opened t o the atmosphere.


sudden changes i n f l o w s .

p r e s s u r e the

T h i s method avoided

The n i t r o g e n was then turned o f f .

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

order to determine the

diluted

was

t i t r a t e d , and

acetylene produced

known amount o f warm 0 . 7

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

Acetylene Absorption Tests

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

^Bubbler packed w i t h g l a s s beads

Table 1.

shows t h a t the most e f f i c i e n t

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

Under these c o n d i t i o n s 96$

a t 5 mole/hr and 95$

of

at 6 mole/hr,

assuming the a b s o r p t i o n a t 1 mole/hr (run d) t o be q u a n t i t a tive.

Cylindrical

bubblers and hot s i l v e r n i t r a t e

were, t h e r e f o r e , used i n the

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

a source o f e r r o r , s i n c e the o u t l e t gases were measured


b e f o r e the a c e t y l e n e d e t e r m i n a t i o n .
estimated a t 15$

T h i s e r r o r c o u l d be

on the assumptions t h a t at the

o f the run the water In the Wet

beginning

T e s t Meter i s a c e t y l e n e

f r e e , and at the end o f the run i s s a t u r a t e d w i t h a c e t y l e n e


f o r i t s p a r t i a l p r e s s u r e In the gas.

However, because o f

the r e l a t i v e poor mixing o f water and gas


and the time allowed
t i o n s before

small and consequently

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

where carbon d i o x i d e was


hydroxide

Test Meter

f o r the gases to flow under steady

s t a r t i n g the run proper,

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

s o l u t i o n , carbon monoxide by o x i d a t i o n w i t h hot


methane by o x i d a t i o n over a hot

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

the gas a n a l y s i s can be found under

Appendix.

Homogeneity o f the

Reaction

In order to i n v e s t i g a t e the homogeneity o f the


r e a c t i o n on an alundum s u r f a c e , the surfce-to-volume r a t i o
of the r e a c t o r was
constant

v a r i e d from 3 . 6 to 24.6

cm" ,
1

maintaining

the f r e e volume o f the r e a c t o r , the f e e d r a t e s o f

methane and n i t r o g e n , the r e a c t i o n temperature and the


t i o n pressure.

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

constant and that except f o r minor changes i n

the o u t l e t flow r a t e , the r e a c t i o n time was

a l s o kept constant

The v a r i a t i o n i n surface-to-volume r a t i o was

accom-

p l i s h e d by i n t r o d u c i n g alundum p e l l e t s i n the r e a c t o r and


i n c r e a s i n g i t s l e n g t h to o b t a i n the same f r e e r e a c t o r volume.

Results

The data used i n the d e t e r m i n a t i o n o f the s u r f a c e


to-volume r a t i o o f the r e a c t o r f o r the i n v e s t i g a t i o n of the
homogeneity of the r e a c t i o n appear under "Reactor Data f o r
Surface-to-Volume

R a t i o Runs" o f the

Appendix.

The r e s u l t s o f the surface-to-volume r a t i o runs,


c a r r i e d out at a r e a c t i o n temperature
pressure o f 1.00

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

of the surface-to-volume r a t i o on the t o t a l c o n v e r s i o n


methane to acetylene
p a r t i a l pressure

and

to carbon, f o r an i n i t i a l methane

of approximately 0.326 atm

time of approximately 0.0248 sec.


conversion
F i g u r e 2,

of

The

and a r e a c t i o n

p l o t o f t o t a l methane

v s . surface-to-volume r a t i o which appears


shows t h a t an i n c r e a s e o f n e a r l y 700%

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

or more o f the f o u r p o s s i b i l i t i e s g i v e n below.

There i s evidence i n support

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

than i n a) above, but

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

T h i s would mean that the average r a t i o

of

alundum s u r f a c e to r e a c t o r volume would be lower than the


initial

and,

t h e r e f o r e , the e f f e c t o f the alundum s u r f a c e

the r e a c t i o n would be l a r g e r than t h a t shown i n F i g u r e

2.

on

18

tO

IS

20

Surface to volume ratio

Figure 2, The percentage


surface-to-volume

conversion of methane
ratio

2S

(cm' )
1

versus the

c) Heat t r a n s f e r to the gas

is controlling, i.e.

i n the packed r e a c t o r , assumed to be at a uniform


t u r e , the Reynolds number and

tempera-

the s u r f a c e area a v a i l a b l e

f o r heat t r a n s f e r are i n c r e a s e d , thus making the gas


erature higher

temp-

( c l o s e r to the r e a c t o r temperature) than

when the r e a c t o r i s unpacked.

The

s l i g h t l y i n c r e a s e d temp-

e r a t u r e would account f o r the h i g h e r

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

the center o f the r e a c t o r where the thermocouple

i s l o c a t e d and,

consequently,

c o n v e r s i o n would correspond

i n the packed r e a c t o r the


to an average temperature highe

than the one measured.

E f f e c t of Carbon

Deposition

In order to i n v e s t i g a t e the e f f e c t which the


carbon d e p o s i t e d i n s i d e the r e a c t o r c o u l d have on the
t i o n , the products
minutes, without
reactor.

The

reac-

were determined at i n t e r v a l s o f about

20

removing the carbon d e p o s i t e d i n s i d e the

f e e d r a t e s of methane and hydrogen, the

reac-

t i o n temperature and the r e a c t o r pressure were kept constant.

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

Included i n Table 3 are the r e s u l t s

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

1.00 atm i n a r e a c t o r o f 13.1

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 ,

from the percentage

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.

On the other hand, a t the lower methane p a r t i a l p r e s s u r e s , the


hydrogen and methane c o n c e n t r a t i o n s were so low t h a t the a n a l y s i s gave i n a c c u r a t e r e s u l t s .

F o r these reasons, the r e s u l t s

obtained f o r the i n t e r m e d i a t e methane p a r t i a l p r e s s u r e s

(0.221,

0 . 3 3 6 , 0.485 atm) w i l l be g i v e n more weight than those o b t a i n e d


f o r the h i g h and low methane p a r t i a l pressures

(O.672,

0.100

atm).

The p a r t i a l p r e s s u r e s o f methane recorded i n Table 5


are shown i n g r a p h i c a l form i n F i g u r e 4 .
decomposition

o f methane was determined

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

p a r t i a l p r e s s u r e s o f methane by e x t r a p o l a t i n g t o zero time.


The f i r s t

order r e a c t i o n r a t e constants

(k ) calculated f o r
Q

t h e ' v a r i o u s curves are as f o l l o w s :

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

The v a l u e s c a l c u l a t e d f o r the r e a c t i o n r a t e constant


are s u f f i c i e n t l y s i m i l a r

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

ot various initial methane partial

versos reaction time

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 -

the average value o f k

constants

would be

which compares w e l l w i t h the value of 1.66

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

* y i e l d e d , f o r each value of the

i n i t i a l p a r t i a l pressure o f methane, a s t r a i g h t l i n e whose


slope k^ i n c r e a s e d w i t h the value of the i n i t i a l methane part i a l p r e s s u r e , and c o u l d be r e p r e s e n t e d approximately

by

the

equation
(12)

= 4.80

( 1 + P0CH4

seer

which means that the methane p a r t i a l pressure c o u l d be

correl-

ated as a f u n c t i o n o f r e a c t i o n time and i n i t i a l methane p a r t i a l


pressure

by

P0H

(13)

= PoCH

.-><

1+

P o C H

4 >*

F i g u r e 4 shows a comparison of experimental

values

of the methane p a r t i a l pressure and values c a l c u l a t e d from the


above

formula.

On the p l o t of acetylene p a r t i a l preasure v s . time


(Figure 5) the r a t e o f change of the acetylene p a r t i a l
was

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 shows the c a l c u l a t e d r a t e s i n atm/sec w i t h the c o r r e s ponding methane and a c e t y l e n e p a r t i a l p r e s s u r e s .

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

l i n e s o f s i m i l a r slope f o r the v a r i o u s constant p a r t i a l p r e s sures of a c e t y l e n e .

S i m i l a r l y , a p l o t o f the r a t e of change

of the a c e t y l e n e p a r t i a l pressure v s . the a c e t y l e n e

partial

p r e s s u r e presents s t r a i g h t l i n e s o f s i m i l a r slope f o r constant


methane p a r t i a l p r e s s u r e , i n d i c a t i n g a r a t e equation o f the
form

PC2H2

(14)

k2

PCH

PC2H2

where the constants were found to have the f o l l o w i n g average


values:
(15)

= 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

(14) can be i n t e g r a t e d to o b t a i n the

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^

S u b s t i t u t i o n i n t h i s equation of the values determined f o r k^,


k ,
2

and k^, however, d i d not reproduce the experimental

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

i s o f the same form as E q . (17)

0.00586 t a k i n g the p l a c e o f

/(kT_

with

+ k ^ ) , and 32.3 - k-^ t a k i n g

the p l a c e o f k^, but i t r e p r e s e n t s the r e s u l t s q u i t e w e l l , as


can be observed

i n F i g u r e 5

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 p r e s sure d e r i v e d from Eq. (21)

(22)

dpQ^jjjj
= (0.00586)(32.3) P C H 4 + (32.3 - kx)

d i f f e r s i n form from Eq. (14) i n t h a t k

PC H
2

i s a constant, whereas

32.3 - k^ depends on the v a l u e o f the i n i t i a l methane

partial

pressure.

In s p i t e o f the good c o r r e l a t i o n obtained f o r the


acetylene pressure-time

curves, o n l y k

(or the c o e f f i c i e n t o f

the methane p a r t i a l pressure i n the r a t e equation) has a c l e a r


t h e o r e t i c a l s i g n i f i c a n c e , s i n c e i t expresses

the dependence o f

the r a t e o f formation o f acetylene on the p a r t i a l p r e s s u r e o f


methane when the p a r t i a l pressures o f acetylene and hydrogen
are z e r o .

The i n c r e a s e i n the r a t e o f a c e t y l e n e formation

with

the p a r t i a l pressure o f a c e t y l e n e may h o l d t r u e o n l y over the


l i m i t e d range i n i/ihich these experiments

were c a r r i e d

out,

s i n c e , a c c o r d i n g t o the r a t e equation, the a c e t y l e n e p a r t i a l


pressure would i n c r e a s e i n d e f i n i t e l y , whereas e q u i l i b r i u m
c a l c u l a t i o n s show t h a t the f i n a l a c e t y l e n e p a r t i a l

pressure

would be o f the order o f 0.003 atm f o r the c o n d i t i o n s o f the


p r e s e n t experiments.

Obviously the r a t e e q u a t i o n would not

h o l d t r u e a t zero methane p a r t i a l pressure s i n c e , a t 1200C


a c e t y l e n e decomposes almost

q u a n t i t a t i v e l y t o carbon and hydr-

ogen, t h e r e f o r e , k^ (or the c o e f f i c i e n t

o f the a c e t y l e n e par-

t i a l p r e s s u r e i n the r a t e equation) d e s c r i b e s o n l y the autocatalytic

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 .

In the r e a c t i o n mechanism proposed

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

c o n t a i n s the term - k ^ ( C H ) which accounts f o r the decrease i n


2

a c e t y l e n e p a r t i a l pressure i n the l a t t e r stages o f the r e a c t i o n

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

I s t h e r e f o r e , e m p i r i c a l and v a l i d only i n the range

of p a r t i a l p r e s s u r e s and r e a c t i o n times o f these

experiments,

f o r which the r e a c t i o n appears t o be i n i t s e a r l y stages and


the r a t e o f decomposition

o f acetylene i s n e g l i g i b l e with

respect to i t s rate o f formation.

In the d e r i v a t i o n o f the formula f o r the r a t e o f


decomposition o f methane from h i s proposed mechanism, K a s s e l
has assumed under the steady s t a t e treatment, t h a t the concent r a t i o n o f a c e t y l e n e i s s m a l l compared t o those o f methane and
hydrogen,

and then, the r a t e o f change o f a c e t y l e n e concen-

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

./has. p o i n t e d out that i n the s t a t i c method

used by K a s s e l , the p r e s s u r e increase* i n the r e a c t i o n v e s s e l


corresponds not t o the r a t e o f decomposition ofmethane, but
to the r a t e o f f o r m a t i o n o f e t h y l e n e , on the assumption
ethane, a c e t y l e n e , and hydrogen
reaction.

are the main products o f the

However, the p r e s e n t experiments

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

and then the pressure i n c r e a s e corresponds v e r y c l o s e l y t o


the r a t e o f decomposition of methane, s i n c e
(26)

dp

dt

d(CH )

dt
4

d(C H )
- 2
dt
2

d(C H )

dt
2

I f the main products o f the r e a c t i o n

arecarbon,

hydrogen, and a c e t y l e n e , the p a r t i a l pressure o f hydrogen may


be expressed as :
P

1 2 7

OCHA-

PCHA

1 ? P O C H *

where the f i r s t term r e p r e s e n t s the p a r t i a l p r e s s u r e o f hydrogen i f methane r e a c t e d o n l y a c c o r d i n g to

Substitution

Eq.(25).

i n Eq.(27) o f the e x p r e s s i o n s p r e v i o u s l y o b t a i n e d f o r the


p a r t i a l p r e s s u r e s o f methane and a c e t y l e r e from Eq.(13) and (20)
g i v e s a n . e q u a t i o n f o r the p a r t i a l p r e s s u r e o f hydrogen which
approximately reproduces

the pressure-time

curves.

However,

the p a r t i a l p r e s s u r e o f hydrogen was best c o r r e l a t e d a s :

(2S)

PH =
*

\ ! . e- '
[
5

1 + POCH^

2 P 0 C H

*]
)

F i g u r e 7 shows a comparison o f the experimental v a l u e s f o r the


hydrogen p a r t i a l p r e s s u r e , and those c a l c u l a t e d from

Eq.(28).

Limitations

The experiments

which form the b a s i s f o r t h i s

study, were c a r r i e d out under c o n d i t i o n s which might a f f e c t


the v e r a c i t y o f the arguments presented above or the v a l i d i t y
of the c o n c l u s i o n s t o be drawn from these arguments.

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)

As evidenced by the t r a c e s o f carbon monoxide

found i n the o u t l e t gases, the feed t o the r e a c t o r was

con-

taminated w i t h f o r e i g n m a t e r i a l such as oxygen, water, o r


carbon d i o x i d e , whose e f f e c t on the r e a c t i o n i s unknown.

2)
of methane was

Although i t was

found that the decomposition

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-

pensate f o r the v a r i a t i o n i n the nature of the s u r f a c e

during

a run.

3)

Except i n the runs s p e c i f i c a l l y made t o i n v e s -

t i g a t e the e f f e c t o f carbon d e p o s i t i o n , the r e a c t i o n times


were c a l c u l a t e d f o r the r e a c t o r volume at the b e g i n n i n g o f the
run and, t h e r e f o r e , not c o r r e c t e d f o r the carbon d e p o s i t i o n .

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

f l a s k at the o u t l e t o f the r e a c t o r were d i s r e g a r d 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

a b s o r p t i o n i n the water o f the Wet


absorption

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 the s i l v e r n i t r a t e s o l u t i o n were not t a k e n

i n t o account.

6)
and

i n the gas

all

times.

The

gases i n the r e a c t o r , i n the Wet

Test

Meter,

a n a l y s i s set were assumed to behave i d e a l l y at

Conclusions

Should the aforementioned l i m i t a t i o n s prove t o


immaterial to the r e s u l t s o f the experiments, the
conclusions
at

be

following

can be drawn about the decomposition o f methane

1200C:

1)

The

r e a c t i o n proceeds homogeneously on a carbon

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

average r e a c t i o n r a t e constant of 5 . 7 s e c "

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

1. K a s s e l , L . S . , J.Am. Chem. S o c , 54, 3949 (1932).


2. S t o r c h , H.H., J . Am. Chem. S o c , 54, 4188 (1932).
3. B e l c h e t z , L . and R i d e a l , E.K., T r a n s . Faraday S o c ,
30, 170

(1934).

4. R i c e , F.O. and Dooley, M.D.,

J . Am. Chem. S o c ,

56, 2747 (1934).


5. R i c e , F.O., J . Am. Chem. S o c , 6 l , 213

(1939).

6. Gordon, A.S., J . Am. Chem. S o c , 70, 395 (1948).


7. Robertson, A.J.B., Proc. Roy. S o c , A 199, 394 (1949).
8. R i c e , F.O. and H e r t z f e l d , K.F., J . Am. Chem. S o c ,
56, 284 (1934).

9. Schoch-, P., U n i v . Texas P u b l . , 5011 (1950).


10. Sachsse, H., P h y s i k . Chem., B 31,

87 (1935).

11. Wulff Process Co., F r . 241 (1939).


12.

Watt, L . J . , The P r o d u c t i o n o f Acetylene from Methane by


P a r t i a l Oxidation, Univ. B r i t . Col.- (1951).

13.

L a i d l e r , K.J., Chemical K i n e t i c s , McGraw-Hill Book


Company, Inc., New York,

(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

I n l e t flow r a t e s from flow meter . c a l i b r a t i o n s :


Pressure Drop
(in.

. CH
. N

Downstream Pressure

H 2 0).

(in.

6.00
7.90

Hg)

. (g-mole/hr)

32.0

. .

32.0.

Outlet flow r a t e from volume-time

measurements:

1.000

Temperature

76P = 535R

Pressure

28.1 - 0.9 = 27.2

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

was d i l u t e d t o 500 ml and 50 ml o f I t r e q u i r e d 3 8 . 3 ml o f


O . I 6 4 N of potassium thyocyanate s o l u t i o n .
Initial AgN0
Pinal AgN0

(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

C o r r e c t i o n f o r methane i n CuO tube

(2.0)(27.1)
(92.5)

Q m 6

'

I n l e t flow r a t e c a l c u l a t e d from the o u t l e t flow r a t e and the


o u t l e t gas a n a l y s i s j on the b a s i s o f the r e a c t i o n s :
2 CH
CH

t 3 ^

C + 2 H

C H

Methane converted t o a c e t y l e n e
2

(0.0147) = 0.0294 g-mole/hr

Methane converted t o carbon and hydrogen


0.43 - 3 (0.0147)
2

= 0.195 g-mole/hr

I n l e t flow r a t e o f methane
1.70

+ 0.0294 + 0.195 = 1.924

g-mole/hr

which compares w e l l w i t h I . 9 6 from the f l o w meter


Conversion o f methane t o a c e t y l e n e
(0.0294)(100)/(i.924) = 1.53 %

calibration.

Conversion o f methane to carbon and hydrogen


(0.195)(100)/(1.924) = 10.2 %
T o t a l c o n v e r s i o n o f methane
1.53 - 10.2 = 11.7 %
The o u t l e t flow r a t e o f n i t r o g e n 3.96 g-mole/hr
compares w e l l w i t h the i n l e t flow r a t e o f 3*92 g-mole/hr from
the flow meter c a l i b r a t i o n .
T o t a l Inlet flow rate
3.96

- 1.924 = 5.88 g-mole/ h r

(6.12

- 5.88)/2 = 6.00 g-mole/hr

Average flow r a t e

Reaction time f o r the r e a c t o r volume o f 5*0 ml and the m o l a l


volume o f 121,000 ml/g-mole:
(5.0)(3600)/(6.00)(121,000) = 0.0248 sec
I n i t i a l p a r t i a l pressure o f methane:
1.924/5.88 = 0.328 atm

Reactor Data f o r Surface-to-Volume

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-