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IHEMISTRY A N D M A N U F A C T U R E
OF
H T D R O G E N
BY
P. L l T H E R L A N D T E E D
\R is MjMlNINC* AND METALLURGY), A I M M
MAJOR, KAI-,
LONDQ.
E D W A R D 1
1919
DEDICATECBTO
M ^ I T L A N D . J L M . G , D.S.O., R.A.F
ANI>
. A-F.C, R . A F .
DEFACE.
P. L. T
EYNSKORD, KENT
CONTENTS.
CHAP. PAGE
I. HYDROGEN—ITS USES—DISCOVERY, AND OCCURRENCE
IN NATURE I
T h e U s e s of H y d r o g e n . — T h e commercial pro-
duction of h y d r o g e n has received a great stimulus dur-
ing the last few years owing to its being required for
industrial a n d war purposes in quantities never previously
anticipated.
T h e discoveries of M. Sabatier with regard to t h e
conversion of olein and other unsaturated fats and their
corresponding acids into stearin or stearic acid have
created a n enormous demand for hydrogen in every in-
dustrial c o u n t r y ; 1 the synthetic production of ammonia
by t h e H a b e r process has produced another industry
with great hydrogen requirements, while the Great W a r
has, t h r o u g h the development of the kite balloon and
airship, m a d e requirements for hydrogen in excess of
t h e two previously mentioned industries combined.
T h e increase in hydrogen production has modified
t h e older processes by which it was made, and has also
led to t h e invention of new processes, with the result
t h a t t h e cost of production has decreased and will prob-
ably continue to decrease, thus allowing of its employ-
ment in yet new industries.
1
The weight of oil hardened by mean&xSBk*.fliQKenin Europe
in 1914 probably exceeded 250,000 tons.
I
2 HYDROGEN
T h e Discovery of H y d r o g e n . — T h e discovery of
hydrogen should b e attributed to T u r q u e t d e Mayerne, 1
who in 1650 obtained, b y the action of dilute sulphuric
acid on iron, a gas, or " inflammable air,", which we now
know to have been hydrogen.
T u r q u e t de M a y e r n e recognised thergpf he obtained
as a distinct substance. Robert B o y l e 9 made some
experiments with it, b u t many of its m o r e important
properties were not discovered until Cavendish's investi-
gations, 8 beginning in 1 7 6 6 ; while the actual name
" H y d r o g e n , " m e a n i n g " w a t e r former," was given to
t h e g a s by Lavoisier, w h o may be r e g a r d e d as the first
philosopher to recognise its elemental n a t u r e .
Occurrence in N a t u r e ,
H y d r o g e n occurs in small quantities in Nature in
the uncombined state. It is found in a state of con-
densation in many rocks and in s o m e specimens of
meteoric iron. It is present in t h e gaseous discharges
from oil and g a s wells a n d volcanoes, a n d is also a con-
stituent to a very m i n u t e extent of t h e atmosphere.
Hydrogen in the uncombined s t a t e exists in enor-
mous masses upon t h e sun, a n d is p r e s e n t in the
" p r o m i n e n c e s " observed in solar eclipses, while by
optical means it may also be detected in m a n y stars and
nebulae.
1
Paracelsus, in a similar experiment in the sixteenth century,
obtained the same gas, but failed to recognise it as a distinct sub-
stance.
2
" New Experiments touching the Relation between Flame and
Air," by the Hon. Robert Boyle, 1672.
8
James Wat^^discoverer of the steam engine, did many similar
experirffl^^^^^^^game time, but his interpretation of his results
Was r ^ j j f f i ^ ^ y ^ ^ ^ f e l
OCCURRENCE IN N A T U R E 3
D
MetSrite.°f Weight Taken. Hydrogen Evolved.
1(
'Proc. Roy. Soc," 1897.
4 HYDROGEN
99-88
%
From Kilattea :—
Hydrogen 10*2
Oxygen . —
Nitrogen II*8
Carbon dioxide 73 9
„ monoxide 4-0
Sulphur dioxide. . . . . . —
99'9
1
R. W Bunsen, " Annales Chim. Phys.," 3rd ser., vol. 38, 1853
2
H . Moissan^^Comptes Rend.," vol. 135, 1902.
8
A. L. Day*andE. S Shepherd, "Bull. Geol. Soc. America,"
vol. 24,
OCCURRENCE IN N A T U R E 7
From Santonn1:—
Hydrogen . 29 43
Oxygen . -32
Nitrogen 32*97
Carbon dioxide . . . . . . 36 43
Carbon monoxide . . . . . —
Methane . -86
Sulphuretted hydrogen . . . —
100 00
!>530
I
:525
520
" r s i
t o b e a n t i c i p a t e d t h a t s u c h a c t i o n , if it t o o k p l a c e , w o u l d
of necessity be relatively slower.
T h e temperature of ignition of v a r y i n g m i x t u r e s o f
hydrogen and oxygen has been most carefully studied
1
by Professor H . B. D i x o n , who, besides much very in-
g e n i o u s a p p a r a t u s , e m p l o y e d t h e c i n e m a t o g r a p h for ob-
taining c o n c l u s i v e e v i d e n c e of t h e conditions p r e v a i l i n g
during explosion.
1(
'Jour. Chem S o c , " vols. 97 and 98, and vols 99 and 100
CHEMICAL PROPERTIES 13
T h e Q u a n t i t y of Heat Produced by B u r n i n g
H y d r o g e n . — T h e t e m p e r a t u r e of ignition a n d the flame
temperature of h y d r o g e n h a v e already been considered.
It now o n l y remains for the quantity of h e a t produced
by a g i v e n weight of hydrogen to be considered in
comparison with s o m e other gases combustible in air.
1
In the case of Zeppelin airships brought down in flames, it is
not surprising that considerable amounts of molten metal have been
found in the locality, observing that the melting point of aluminium
is 6570 C, copper 10870 C.
2
Fery, le
3
Fery, / c. The temperature of acetylene burning in oxygen is
about 40000 C , but this arises from circumstances not present in the
case of hydrogen flames
4
Le Chatelier.
2
18 HYDROGEN
Chemical C o m b i n a t i o n of H y d r o g e n w i t h Chlorine,
B r o m i n e , and Iodine.
W i t h C h l o r i n e . — H y d r o g e n will c o m b i n e with
chlorine, in accordance with t h e following chemical
equation, to m a k e hydrochloric acid :—
H a + Cl2 = 2HCI.
If the two g a s e s are mixed in equal proportions in a
diffused light a n d are subjected to a n electric spark, the
above reaction takes p l a c e with explosive violence. If
a glass t u b e containing a m i x t u r e of t h e g a s e s is heated,
the s a m e reaction takes place with violence.
If a mixture of h y d r o g e n a n d chlorine at atmospheric
t e m p e r a t u r e is exposed t o s t r o n g sunlight, hydrochloric
acid is immediately formed, with t h e characteristic ex-
plosion. Investigation of this increase in t h e chemical
activity of h y d r o g e n a n d chlorine in t h e presence of
sunlight h a s shown t h a t it is t h e actinic rays which pro-
duce the p h e n o m e n o n ; t h u s if t h e r a y s which are p r e s e n t
at the blue a n d violet e n d of t h e s p e c t r u m a r e p r e v e n t e d
from r e a c h i n g t h e m i x t u r e of t h e gases b y protecting
this b y a red glass screen, n o reaction b e t w e e n t h e m
takes place. W h e n sunlight is n o t available, t h e ex-
plosive combination of these t w o g a s e s can be s h o w n
by exposing a mixture of t h e m in a glass vessel to the
light of b u r n i n g m a g n e s i u m , such a s is frequently used
by photographers.
T h e r e m a r k s which h a v e a l r e a d y b e e n m a d e with
regard t o t h e reduction in chemical activity of h y d r o g e n
22 HYDROGEN
FIG 2.
Insolation Vessel
W i t h S e l e n i u m . — W h e n selenium is h e a t e d to 250°
I. with h y d r o g e n , chemical union results, with t h e pro-
uction of selenuretted h y d r o g e n .—
H 2 + Se - H2Se
T h e resulting g a s is colourless, r e s e m b l i n g sul-
huretted h y d r o g e n in smell a n d in its chemical proper-
es. It is, however, m u c h m o r e poisonous t h a n the
)rmer g a s .
S e l e n u r e t t e d h y d r o g e n is inflammable a n d b u r n s in
le same w a y a s s u l p h u r e t t e d h y d r o g e n . If the g a s is
:rongly h e a t e d it b r e a k s u p into its t w o constituents,
le selenium b e i n g deposited in the crystalline form.
Selenuretted h y d r o g e n is soluble in water at 13*2° C.
) the extent of 3 31 p a r t s b y volume p e r unit volume of
ater.
T h e density of s e l e n u r e t t e d h y d r o g e n is 40*5 times
lat of h y d r o g e n .
26 HYDROGEN
commercial scale in G e r m a n y , is k n o w n as t h e H a b e r
process, b u t few details as to t h e m e t h o d of operation
are available. I n t h e earlier s t a g e s of t h e working of
this process the catalytic a g e n t w a s probably osmium,
but it is considered doubtful if this is still being em-
ployed.
THE U S E S OF AMMONIA.
PROPERTIES OF A M M O N I A .
2 NH 3+ H2SO4 = (NH4)2SO4,
NH 8 + HC1 - (NHJCl,
NH 3 + HNOa = (NH4)NO3
Grammes of NH3 C c of Nl
Temperature. Dissolved in 1 c.c
of Water. 0 \J and 7c
showed a g r e a t resistance t o t e a r i n g . T h e d a m a g e d
spots w e r e found to b e i m p r e g n a t e d with phosphoric
acid and a r s e n i c acid, p r o d u c e d b y t h e oxidation of the
phosphine a n d arsine contained in t h e h y d r o g e n with
which the balloon h a d b e e n inflated.
Phosphine in small quantities in h y d r o g e n contain-
ing over 1 p e r cent, of o x y g e n a t t a c k s copper, producing
an acid liquid which h a s a m o s t corrosive action on
fabric. H o w e v e r , it does not a p p e a r u n d e r these cir-
cumstances t o h a v e a n y action o n aluminium or zinc ;
consequently a n y m e t a l p a r t s inside t h e envelope of
a n airship should b e of aluminium. P h o s p h i n e under
the above conditions a t t a c k s h e m p a n d o t h e r textiles
which h a v e b e e n t r e a t e d with copper compounds,
b u t it does not a p p e a r to h a v e a n y action on fabrics
free from copper c o m p o u n d s or copper or brass
fastenings.
T h o u g h it has b e e n stated t h a t phosphine, is not
spontaneously inflammable, with quite small admixtures
of liquid h y d r o g e n p h o s p h i d e it immediately bursts into
flame on c o m i n g into contact with air.
Phosphine p r o d u c e d b y t h e reaction of water on
calcium phosphide always contains a q u a n t i t y of the
liquid h y d r o g e n p h o s p h i d e sufficient t o m a k e the g a s
spontaneously inflammable. U s e of this property is
m a d e in t h e H o l m e s ' L i g h t used a t s e a a s a distress
signal, a n d also as a m a r k e r a t t o r p e d o practice.
Phosphine is soluble in water to a slight extent.
T h e solution of phosphine in w a t e r is not very stable,
particularly in s t r o n g light, w h e n it b r e a k s up, deposit-
i n g red p h o s p h o r u s .
T h e d e n s i t y of p h o s p h i n e is 17*5 times that of
hydrogen.
32 HYDROGEN
Zhemical C o m b i n a t i o n of H y d r o g e n w i t h Animal
a n d V e g e t a b l e Oil.
T H E MANUFACTURE OF HYDROGEN.
CHEMICAL METHODS.
(1) M e t h o d s U s i n g an Acid,
W i t h Iron.—If dilute sulphuric acid is b r o u g h t into
contact with iron, chemical action takes place, with t h e
production of h y d r o g e n a n d ferrous sulphate, in accord-
ance with the following equation :—
Fe + H2SO4 « H2 + FeSO4.
Theoretically, to produce 1000 cubic feet of hydrogen
at 30 inches barometric pressure a n d 40° F . b y this pro-
cess, 155 Ib. of iron a n d 272 lb. of pure sulphuric acid a r e
CHEMICAL METHODS 41
(2) M e t h o d s U s i n g an Alkali,
W i t h Zinc*—If a solution of caustic soda in water
is b r o u g h t into contact with metallic zinc, chemical
reaction t a k e s place, with t h e production of sodium
zincate a n d h y d r o g e n . T h e reaction is expressed in
the following equation :—
Zn + 2NaOH => H 2 + Na2ZnC>2.
Theoretically, to produce 1000 cubic feet of h y d r o -
gen at 30 inches barometric pressure a n d 40° F . , 180 lb.
of zinc a n d 224 lb. of p u r e caustic s o d a a r e required, or a
total weight of p u r e r e a g e n t s equal t o 404 lb. p e r 1000
cubic feet of h y d r o g e n produced.
T h e h y d r o g e n p r o d u c e d b y this process is generally
very pure, but, d e p e n d i n g on the purity of the zinc, it is
liable to contain arsine. A s t h e g a s is alkaline, owing
to the caustic s o d a carried in suspension, it requires to
b e scrubbed to m a k e it suitable for balloons a n d air-
ships.
A modification of this process h a s been the subject
of a patent. Zinc as a fine powder is mixed with dry
44 MANUFACTURE OF HYDROGEN
r e q u i s i t e q u a n t i t y of c a u s t i c s o d a is p l a c e d in t h e t a n k
o n t h e r i g h t a n d t h e n e c e s s a r y w a t e r a d d e d t o it t o m a k e
a 25 p e r cent, s o l u t i o n . T o a s s i s t s o l u t i o n t h e r e is a
s t i r r e r i n this t a n k , w h i c h , in s m a l l p l a n t s , is h a n d - o p e r -
a t e d a n d in l a r g e o n e s p o w e r - o p e r a t e d . W h e n the whole
of t h e c a u s t i c s o d a h a s g o n e i n t o s o l u t i o n , w h i c h it r e a d i l y
CHEMICAL METHODS 49
0 ID 20 30 40 50 60 70 80 90 100%
Silicon in Ferrosilicon
FIG. 4
I I
JU-! i i
^ >
1/
f
J /
6& D
I 12 14- 16 18
Time in Minutes
20 22 Z4- 26 28 30
FIG. 5.
52 MANUFACTURE OF HYDROGEN
I
1 i to 0426 1 to 1*52 4'9S
2 1 „ 0426 1 „ 272 15-95
3 1 „ 0-426 1 „ 3 04 15-23
1
Standard I M.M. screens,
CHEMICAL METHODS 57
Temperature
rf
Volume of Hydrogen
C. per Hour.
W i t h C a l c i u m H y d r i d e , — I f calcium h y d n d e is
j g h t into contact with water, h y d r o g e n is evolved
68 M A N U F A C T U R E OF HYDROGEN
W i t h A l u m i n i u m A l l o y * — T h e following a l l o y —
Aluminium . . . 78-98 parts
Zinc . 15-15 »
Tin . .7-05 »
is m a d e a n d cast into a p l a t e ; after cooling it is a m a l g a -
mated with mercury. After a m a l g a m a t i o n t h e p l a t e is
heated a s strongly as possible without volatilising t h e
mercury. W h e n it has become thoroughly a m a l g a m a t e d
it is allowed to cool a n d is then ready for use.
If this alloy is put into hot water it readily yields
hydrogen ; the h y d r o g e n yield is proportionate t o t h e
aluminium a n d zinc content.
T h e g a s produced is very pure.
T h i s process is protected by the following p a t e n t
U y e n o , ' B r i t i s h patent, 11838, 1912.
W i t h Steam.
T H E MANUFACTURE OF W A T E R GAS.
T h e m e t h o d of w o r k i n g this g e n e r a t o r would b e as
follows :—
W h e n a c o k e o r o t h e r fire of suitable d e p t h h a s b e e n
obtained o n t h e g r a t e , t h e receptacle B is c h a r g e d
with fuel, a n d t h e lid C firmly closed ; v a l v e s I a n d
I ' a r e closed a n d v a l v e F opened, t h e n air u n d e r
suitable p r e s s u r e is a d m i t t e d t h r o u g h L a n d G ; this
causes t h e fuel to b u r n with rise in t e m p e r a t u r e of
t h e u n b u r n t portion, while the p r o d u c t s of combus-
tion, containing a b o u t 20 p e r cent, of carbon dioxide
a n d 70 per cent, of nitrogen, escape by t h e p a s s a g e E .
W h e n t h e t e m p e r a t u r e of the coke on the hearth has
b e e n raised to a b o u t i o o o 0 C. the air blast is stopped,
v a l v e F closed, v a l v e I ' opened, a n d s t e a m a d m i t t e d
t h r o u g h S ' with t h e c o n s e q u e n t production of blue g a s ,
which passes out t o a scrubber a n d holder, via the
valve I'.
W h e n a s a result of t h e decomposition of t h e steam
by the fuel mass, the t e m p e r a t u r e of the latter h a s fallen
below the economic limit, t h e steam supply is s h u t off,
a n d the air blast started again to raise t h e fuel t e m p e r a -
ture. W h e n t h e t e m p e r a t u r e is a g a i n suitable, t h e air
is shut off a n d steam a g a i n passed t h r o u g h t h e fuel, b u t
o n this occasion d o w n w a r d s from t h e s t e a m supply S,
t h e w a t e r g a s p a s s i n g o u t by t h e outlet I.
T h e object of this alternation of t h e direction of the
s t e a m blast is to k e e p t h e t e m p e r a t u r e as uniform as
possible t h r o u g h o u t t h e fuel mass.
F i g . 7 shows a m o d e r n water g a s producer, which
is self-explanatory, t h e fuel c h a r g i n g is d o n e after
every third s t e a m blast, a n d t h e d e p t h of t h e fuel k e p t
correct by m e a n s of a g a u g e rod, d r o p p e d t h r o u g h t h e
lid at t h e t o p of t h e g e n e r a t o r . T h e s a m e alternation
78 MANUFACTURE OF HYDROGEN
Steam
Inlet
\ Gas Outlet
\~Ash Outlet
FIG 7
= 29*6 lb
But carbon monoxide contains i | of its total weight of carbon.
28
20 6 X 12
.•. 396 cubic feet of carbon monoxide contains „ lb.
carbon = 1 2 7 lb.
Similarly,
1000 cubic feet of carbon dioxide weighs 117 3 lb
35 x " 7 3
• •35 •! » » » » Iooo
= 4 1 lb.
But carbon dioxide contains — of its total weight of carbon.
44
.. 35 cubic feet of carbon monoxide contains lb. of
44
carbon = 1 1 lb
A d d i n g these two results together, it is seen that while
35-40 lb. of coke, equivalent to 29-33 lb. of carbon, a r e
consumed in the generator per 1000 cubic feet of water
gas, only 13 8 lb. of this carbon, or 42-46 per cent., are
present in the g a s produced, the bulk of t h e remainder
of the carbon consumed in the generator b e i n g burnt
during the air blast period, and the remainder lost in the
ash pit, and during clinkering; however, while these
figures are instructive, as indicating the m a g n i t u d e of
air blast consumption of fuel, to gain comparative figures
it is necessary to obtain the calorific power of the coke
CHEMICAL METHODS 81
consumed, a n d of t h a t of t h e w a t e r g a s p r o d u c e d from
a given w e i g h t of coke.
If 35 lb. of t h e coke, t h e analysis of which h a s been
already given, a r e c o n s u m e d in t h e production of 1000
cubic feet of water g a s at 30 inches b a r o m e t e r a n d 6o°
F. f of t h e composition which h a s also been given, it will
b e found t h a t t h e calorific power of t h e coke consumed,
c o m p a r e d w i t h t h a t of the g a s produced, is as
516:342,
t h a t is to say, j u d g e d o n a t h e r m a l efficiency basis, t h e
efficiency of t h e p r o d u c e r w o r k i n g u n d e r these condi-
tions is
342 x 100 _
516
which is a figure such as is obtained in ordinary com-
mercial w a t e r g a s manufacture.
T h e analysis of t h e water g a s so far g i v e n e n u m e r -
ates t h e chief constituents, but in reality t h e r e are traces
of other products, such as carbon bisulphide, carbonyl
sulphide, a n d thiophene, derived from t h e sulphur in t h e
"uel, which, m i n u t e in quantity, m a y nevertheless in the
:ertain chemical processes p r o d u c e appreciable a n d un-
iesirable r e s u l t s : from t h e iron contained in t h e fuel,
n i n u t e a m o u n t s of iron carbonyl a r e formed, which in
n o s t processes in which water g a s is used is a m a t t e r
>f n o importance, b u t if the g a s is to b e used for
i g h t i n g with incandescent mantles, its removal is de-
•irable.
T h e producer, which has been described, is not in
>ractice absolutely continuous in operation, as from
ime t o t i m e t h e process has to b e interrupted in order
o r e m o v e t h e clinker from t h e fire.
6
82 MANUFACTURE OF HYDROGEN
Purification of W a t e r G a s , — F o r m o s t industrial
purposes, it is necessary t h a t the crude w a t e r g a s should
CHEMICAL METHODS
TV
71/
S e c t i o n CD.
FIG 8.
84 M A N U F A C T U R E OF H Y D R O G E N
R e m o v a l of Sulphuretted H y d r o g e n . — F o r most
purposes for which water gas is required it is desirable
t h a t it should b e free from sulphuretted h y d r o g e n , this
is usually accomplished b y passing t h e g a s a t about
55°-65° F . over h y d r a t e d oxide of iron, when the fol-
lowing reaction takes place :—
Fe3(OH)6 + 3H2S = 2FeS + 6HaO + S.
After lapse of time, t h e hydrated ferric oxide ceases to
h a v e a n y sulphuretted hydrogen-absorbing power, so
t h e g a s is diverted t h r o u g h other h y d r a t e d oxide, and
t h e spent oxide r e m o v e d and placed in the open air,
when, after moistening with water a n d exposure, the
following reaction takes place .—
4FeS + 6HSO + 3O2 - 2Fea(OH)<j + 4S
T h u s it is seen the original oxide can b e reproduced,
a n d on reproduction can b e used for t h e absorption of
fresh sulphuretted hydrogen. In practice each revivi-
fication increases t h e free sulphur content of t h e oxide
CHEMICAL METHODS 85
T h e Iron Contact P r o c e s s .
Of all the processes for the production of h y d r o g e n
in which water g a s represents one of the active r e a g e n t s ,
t h e Iron Contact process is the most important, as it is
b y this process t h a t t h e greater a m o u n t of t h e w o r l d
production of h y d r o g e n for use in industry a n d w a r is
at present m a d e ; b u t important as this process is, it is
doubtful if it will maintain its p r e s e n t pre-eminent posi-
tion d u r i n g the next few years, as other processes, m o r e
economical, but at p r e s e n t n o t so reliable, are a l r e a d y in
existence, and with lapse of time g r e a t e r reliability will
p r o b a b l y b e obtained in these later processes, which will
result in the I r o n Contact process occupying a less im-
p o r t a n t position in h y d r o g e n production than it d o e s
to-day.
When steam is passed over h e a t e d metallic iron,
CHEMICAL METHODS 87
56 ^ ^
'60 ^
:« ^
i>40
i
1
„...*-
Weight of Oxide =4-2 tons _
20
.--""" Volume of Water Gae -9000 cu ft per hour
1S " | i i i I l I l I
0 1 2 3 4 5 6 7 8 9 3D 11 1Z 13 14 15 16 17 38
Minutes
FIG 9
Luch slower than the speed of oxidation, consequently,
L practice, t h e duration of the various stages is :—
Reducing . . . . 2 0 minutes.
Purging . . 35 seconds.
Oxidising . . . 9 minutes, 25 seconds.
100 00
IOO'O
I r o n C o n t a c t P l a n t * — T h e fundamental a n d second-
ary chemical reactions involved in this process h a v i n g
been considered, t h e r e remains only t h e plant, a n d t h e
actual fuel consumption per 1000 cubic feet of h y d r o g e n
to b e described.
T h e Iron Contact plant is commercially manufactured
in two distinct types :—
1. T h e Multi-Retort t y p e .
2. T h e Single R e t o r t type.
Fig. 10 shows a purely diagrammatic a r r a n g e -
ment of a multi-retort generator. T h e retorts a r e ex-
ternally h e a t e d b y means of a g a s producer incorporated
in the retort bench. T h e even h e a t i n g of the retorts is
secured by t h e use of refractory baffles (not s h o w n ) a n d
by the admission of air for the proper combustion of t h e
producer g a s a t different points.
94 M A N U F A C T U R E OF HYDROGEN
FIG IO.
FIG II.
W i t h B a r i u m S u l p h i d e . — I n t h e previous process
which was considered, steam was decomposed by means
of spongy i r o n ; in t h e present process, instead of iron,
barium sulphide is used. If s t e a m is passed over bar-
ium sulphide h e a t e d to a bright red heat, the following
reaction takes place :—
BaS + 4H 2 O - BaSO4 + 4H 2 .
T h e barium sulphate p r o d u c e d m a y b e reduced by
heating with coke t o barium sulphide in accordance
with the following equation :—
BaSO4 + C = BaS + 4CO.
T h e barium sulphide can b e e m p l o y e d for the
g e n e r a t i o n of fresh h y d r o g e n a n d t h e carbon monoxide
can be used for s u p p l y i n g a portion of t h e heat which is
required for the process.
T h e process is protected b y F r e n c h p a t e n t 361866,
1905, in t h e n a m e of Lahousse.
A s o m e w h a t similar process to t h e L a h o u s s e has
been protected by F r e n c h p a t e n t 447688, 1912, in the
names of Teissier a n d Chaillaux. In this process bar-
ium sulphate is h e a t e d with m a n g a n o u s oxide, when the
following reaction t a k e s place .—
BaSO4 + 4M11O = BaS + 4MnO2.
T h e resulting m i x t u r e of b a r i u m sulphide a n d m a n -
CHEMICAL METHODS 101
r e d u c i n g t h e q u a n t i t y of s t e a m in t h e i n c o m i n g g a s e o u s
mixture.
The whole apparatus is v e r y effectively lagged to
reduce the heat losses to a minimum.
To Milli -voltmeter
Thermo-couples
for Temperatures
—between 450 & 500'C
Superheater or
Regenerator
Contact
Material
WaterGas
Inlet
Orifice Gauge Diatomite Brick Cover
throughout, bound with
Hydrogen Painted Cloth
and C02
Outlet
To Mi Hi-
voltmeter
FIG i2.
CHEMICO-PHYSICAL METHODS.
Lindc*Frank'Caro P r o c e s s * — T h e m o s t i m p o r t a n t
ethod of producing hydrogen, in which chemical a n d
lysical m e t h o d s are employed, is one in which t h e
emical process results in t h e production of blue w a t e r
s, and t h e physical in t h e separation of t h e chemical
mpounds (chiefly carbon monoxide) from t h e h y d r o g e n
liquefaction.
Gas
" Template Cnfcal Pressure.
1
Discovered by Andrews, 1863
CHEMICO-PHYSICAL METHODS 115
BOILING P O I N T S OF SOME L I Q U I D G A S E S AT A T M O S -
PHERIC PRESSURE.
Caustic Soda Scrubber (NaOH 307J, last traces CO2 & H2S absorbed
In t h e L i n d e - F r a n k - C a r o process t h e b l u e w a t e r
g a s is compressed to 20 atmospheres, a n d under
pressure it is passed t h r o u g h water, which r e m o v e s
CHEMICO-PHYSICAL M E T H O D S 117
ki
s
!
_AJVaterGasIn/et A **i
""* Carbon Monoxide Outlet
D Nitrogen Outlet D.
=njU
u
Liquid Nitrogen Inlet o
°
o
o
o
o
o
o
o
o
0
F I G 13 — D i a g r a m s h o w i n g L i n d e - F r a n k - C a r o Process.
Per Cent,
by Volume
1
H y d r o g e n . . . . 97*0
-
Nitrogen . i o
C a r b o n m o n o x i d e . . 2 0
Sulphuretted h y d r o g e n . . . . . nil.
O r g a n i c sulphur c o m p o u n d s . . —
W h e n t h e g a s i s r e q u i r e d t o b e o f h i g h p u r i t y it is
1
Messrs A r d o l of Selby, Yorks, w h o e m p l o y this process, kindly
D i f f u s i o n . — T h e separation of h y d r o g e n from t h e
ler constituents of blue w a t e r g a s h a s b e e n proposed,
lploying diffusion for t h e purpose. G r a h a m expressed
2 law of diffusion of gases as .—
" T h e relative velocities of diffusion of a n y t w o
ses are inversely as the s q u a r e roots of their densities."
T h a t is to say, if a m i x t u r e of t w o gases of different
nsities is passed t h r o u g h a p o r o u s t u b e , e.g. unglazed
rcelain, in a given time, m o r e of t h e lighter g a s would
ve passed t h r o u g h t h e walls of t h e t u b e t h a n of t h e
avier, or, t o t a k e a concrete example, s u p p o s e t h e
ixture of g a s e s was o n e composed of equal p a r t s b y
•lume of h y d r o g e n a n d o x y g e n , then, since their
nsities a r e as 1 t o 16, a n d since, therefore, t h e roots
their densities a r e as 1 to 4, in a g i v e n t i m e four
nes as much h y d r o g e n would diffuse t h r o u g h t h e
sdium a s o x y g e n .
T h e densities a n d t h e s q u a r e r o o t s of the densities
the constituents of blue water g a s a r e g i v e n below ;—
122 MANUFACTURE OF HYDROGEN
Density. jW
Hydrogen . i 1
Carbon monoxide 14 3*7
,, dioxide 22 47
Nitrogen 14 37
Methane . 8 28
Sulphuretted hydrogen 17 41
Oxygen 16 4'°
PHYSICAL METHODS.
I 1
^ Electrolyte
1
Battery
FIG 14.—Electrolytic Cell.
Hydrogen i i i
Oxygen . . 16 2 8
Gold . . 197 3 or 1 65 6 or 197
Tm . 118 4 „ 2 29-5 „ 59
Phosphorus . 31 5 „ 3 6*02 „ 10-03
Tungsten . . 184 6 ,, 4 306 „ 46 o
11
Zinc bromide i'8o
Cadmium chloride • 1-78 1
Orthophosphonc acid 170 1
Nitric acid 1*69 1
Caustic soda 1 69 11
„ potash . . 1*67 11
Lead nitrate I-S2 1
Hydrochloric acid 1-31 11 1
Silver nitrate 70 1
E C
sz
'bber
9 9
f
H
Porous Partition Electrode Section
on CD.
Section
onE.E
Hydrogen Liberated
! SS S23 3 2 SEE ^ "T
Hydrogen Outlet
Oxygen Liberated
FIG. 15.
Filter P r e s s T y p e , — I f , in t h e d i a g r a m m a t i c cell
:
ig. 15), a p l a t e of c o n d u c t i n g m a t e r i a l w a s placed
•tween t h e a n o d e a n d c a t h o d e a n d t h e c u r r e n t s w i t c h e d
L, h y d r o g e n w o u l d b e l i b e r a t e d a t t h e o r i g i n a l c a t h o d e
d o x y g e n a t t h e o r i g i n a l a n o d e , b u t , b e s i d e s t h i s , it
134 MANUFACTURE OF HYDROGEN
would be found that on the side of the plate facing the
original cathode oxygen would be liberated, while on its
H K
•!-__ _-"»
//_ B B _^H
\ m '' • •
*_ - £ 0 0 0 0 0 --^.,
A
p o o *
Similar Holes frilled
&I1 Wtr CylmderC
-- -—^i ii ail
Hydrogen
Outlet
6lass
Plan View
FIG 19.
Hydrogen Outlet
r ^ X ~ & J
f ~i
"Mercury
FIG. 20—'-Castner-Kellner Cell
m e r c u r y t o t h e n e g a t i v e electrode in t h e c e n t r e c o m p a r t -
ment.
N o w , c o n s i d e r i n g o n e of t h e e n d c o m p a r t m e n t s , b y
t h e s p l i t t i n g u p of t h e s o d i u m c h l o r i d e , c h l o r i n e will b e
l i b e r a t e d a t t h e p o s i t i v e e l e c t r o d e , a n d will u l t i m a t e l y
p a s s o u t a t E , t o b e u s e d for m a k i n g b l e a c h i n g p o w d e r ,
o r for s o m e o t h e r p u r p o s e , w h i l e s o d i u m will b e d e -
p o s i t e d o n t h e m e r c u r y , w i t h w h i c h it will a m a l g a m a t e .
O w i n g t o t h e r o c k i n g of t h e b o x , t h e s o d i u m m e r c u r y
a m a l g a m will p a s s i n t o t h e c e n t r e c o m p a r t m e n t , w h e r e
144 M A N U F A C T U R E OF H Y D R O G E N
APPENDIX.
PHYSICAL CONSTANTS.
PHYSICAL PROPERTIES OF HYDROGEN.
D E N S I T Y OF L I Q U I D HYDROGEN.
LATENT H E A T OF HYDROGEN.
123 cal. per grm,
IO
146 MANUFACTURE OF HYDROGEN
DENSITY OF GASEOUS HYDROGEN.
At o° C. and 760 mm.
•08987 grm. per litre.
5*607 1b. per 1000 cubic feet
SPECIFIC HEAT OF GASEOUS HYDROGEN.
At constant pressure.
At atmospheric pressure . 3'4°2)
30 atmospheres . . 3-788/ Lussana '
At constant volume
At 500 C . . 2 402 (Joly, 1891).
REFRACTIVITY OF HYDROGEN
l ooo
„ . ' ' \ Ramsay & Travers.
Hydrogen . . . -473!
RELATIONSHIP BETWEEN P R E S S U R E AND V O L U M E
aSgggss-gggsgssgs s__s s_
1
Variation per
Atmospheric Pressure.
Air . 1 \
91 6 - 0*203
6 o o 8
Hydrogen '8 + 9
J 6 90-3 + 0-046
B , b
ydrogen - " ' 3 4 * J_*
460 + T
h e r e P =» P u r i t y o f h y d r o g e n b y v o l u m e e x p r e s s e d in percentage.
B = B a r o m e t r i c pressure in inches.
T •» T e m p e r a t u r e of air in degrees Fahrenheit on the dry
thermometer
•5
' ! • 75
•' ' T i l I I I I I \
7 J r r / i i it ii
3 t ' - i , r * w » i i
r J I I / / i l l I I I I I f
20 Z$ 10 35 4p 4S $b 95 60 6ft TO "75 80
Temperature of Dry Thermometer/n F?
F I G . 22.—Correction for Humidity m lb per i o o o Cubic Feet.
a p o s i t i o n w h i c h m a y b e e s t i m a t e d a t '2,6 l b . ; t h e r e f o r e
•36 lb. m u s t b e s u b t r a c t e d f r o m t h e lift p e r 1 0 0 0 cubic
feet of h y d r o g e n as determined b y t h e formula when
t h e t e m p e r a t u r e of t h e air b y t h e d r y t h e r m o m e t e r w a s
6o° F. a n d the difference b e t w e e n w e t a n d dry i o ° F .
INDEX.