40

Steam Naphtha' Reforming By The Imperial Chemical I n d u s t r i e s Process

Raymond J. Kenard , Jr

Joseph C. Maginn
S e l a s Corporation of America
Dresher, Pennsylvania
I n 1803 Thomas Robert Malthus published h i s "Essay on Population" which culminated

a f i v e year study of population growth i n a l l the c o u n t r i e s of the world. Halthue

concluded t h a t population tends t o grow a t a r a t e f a s t e r than the r a t e of growth
of food producing resources and t h a t t h e r e f o r e famines, ware and p e s t i l e n c e were an
unavoidable means of checking t h i s growth. Malthus' p e s s i m i s t i c view of the f u t u r e
was bourne o u t in the 1800's by the Napoleanic wars followed by food shortages i n
Europe and the I r i s h famine of the 1840's.
Some 70 t o 80 years later S i r W i l l i a m Crooks, t h e aminent English chemist who
discovered the element thallium, predicted that the a n t i r e world faced 8 wheat
famine i n 25 years because e x i s t i n g euppliee of nitrogenous f e r U l i z e r s (Chilean
s a l t p e t e r ) would b e exhausted by t h a t time. S i r Crooks s t a t e d : "The f i x a t l o o of
atmospheric nitrogen is one of t h e g r e a t e s t d i e c o v e r i e s awaiting the ingenuity of
chemists". (1)

1
LJ

Now, a f t e r another period of some 70 t o 80 years, a t t e n t i o n is again being d i r e c t e d

t o t h e age o l d problem of producing enough food t o support the world's growing
population. The emphasis has passed, however, from t h e prevention of s t a r v a t i o n t o
maintaining and, hopefully, t o improving the d i e t of undernourished m i l l i o n s , and
a s w e l l a8 t o planning t h e use of raw material resources to feed t h e burgeoning
population of the world. (2)
That t h e emphasis has s h i f t e d r e f l e c t s with c r e d i t upongivances i n science. The
use of manures and composts-for Improving t h e y i e l d of farm products d a t e e from the
e a r l i e s t days of c i v i l i z a t i o n . I n the eecond century before C h r i s t , Cato, i n h i e
book D e re Rustica, d e t a i l e d t h e b e n e f i t s t o be derived from organic f e r t i l i z e r s .
suggesting
Arab echolars i n the 10th Century noted the value of blood a s manure
t h a t human blood was the b e s t kind. American Indians placed f i s h in t h e i r corn h i l l s .

Lacking, however, was the e c i e n t i f i c approach t h a t would iead t o recognition of the

value of inorganic eources of s o i l n u t r i e n t s . Obviously, organic material was l i n i t o d
i n a v a i l a b i l i t y . The f i r s t e c i e n t i f i c e f f o r t s were undertaken by John Bennett Lawes
a t h i s estate, Rothamsted.
L a w s s t u d i e d chemistry a t Oxford and wae well versed i n the t h e o r e t i c a l discussion8

of contemporary chemiets on t h e s u b j e c t of s o f l managemant. He determined to perform

p r a c t i c a l a p p l i c a t i o n work on h i s estate, t a c k l i n g as h i e f i r s t problem t h e making
of water soluble soil n u t r i e n t a .

By extonaive cxperinmntation i n pot8 and then i n the open s o i l of the f i e l d s , W e s

found t h a t bones needed 8 preliminary treatment with a c i d t o c o o s i s t a n t l y achieva

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their maximum effecfiveneyss. In- 1842 he patented a process for treating bones and
rock phosphate with sulfuric acid to make soluble phosphates.
. .
By about 1880, application of Chilean nitrates to the soil was accepted, and
shipment of nit'rates expanded 10 fold in the subsequent 30 years. (3) With this as
the background, the stage was set for some scientist to synthesize ammonia.
One likes to think that the ability to synthesize ammonia opened a new era of well
being for mankind. Unfortunately, nitrogenous compounds were as vitally important
to the waging of war, at least before the atom bomb, as they were to the growing of
food. Within 4 years after successful laboratory synthesis of aaunonia by Fritz
Haber , World War I was declared.
The production of nitrogen from various sources before and after World War I is
shown in Table I. ,
In 1913, production of nitrogen totalled 851 thousand tons. In 1918, production
had increased 38% to 1160 thousand tons. In the same 5 year interval of time,
production of synthetic nitrogen increased 700% from 3% to 167, of the total
product ion.
Germany was the only nation to achieve self-sufficiency in nitrogen required for
both explosives and fertilizers. The United States did not have an annnonia synthesis
plant in production until 1921.
With the importance of fertilizers now scientifically demonstrated, and with
techniques available to synthesize amnonia from the plentiful supplies of nitrogen
in the atmosphere, attention was directed to alternate sources of, and economic
means for recovering, hydrogen.
In these early years, the various sources of hydrogen were limited to byproduct gas
from the electrolysis of brine, byproduct gas from the conversion of coal to coke
and "producer gas" from the reaction of incandescent coke with steam.
Considerable work was being done on the reforming of gaseous hydrocarbons by the
I. G. Farben interests. (4) Basic patents were issued in 1913 and 1927. Following
an exchange of information with Standard Oil Development Company (now Esso Research
C Engineering C o . ) , Standard Oil brought the process to comnercial realization in
1930 with an installation of three reformers at their Bayway, New Jersey Refinery,
Three more installations were made soon thereafter at their Baton Rouge, Louisiana
Refinery. Standard Oil's installations were for the purpose of producing hydrogen
to hydrogenate low quality gasolines, kerosene8 and diesel fuels. It appeared that
hydrogenation of distillate oil stocks would be a major process for all refiners
because of the relatively poor quality crude oils available at the time.
Concurrent with Standard's interest, Imperial Chemical Industries in 1928 undertook
pilot plant studies of steam reforming of gaseous hydrocarbons. These studies led
to a comeercial installation in 1936.
In the latter part of the Thirties, Standard Oil's interest in the process waned as
the need for oil hydrogenation processes failed to materialize. However, IC1 continued their intensive pilot plant vork, as their prime interest was amnonia
production and they recognized the importance of steam reforming in the preparation
of anmonia synthesis gas.
The United States chemical companies were not unaware of the potential for steam
reforming, Both Hercules Powder Company and Atlas Powder Company approached I. G.

-.

42

Farben i n the l a t t e r p a r t of r ' . e 1930's for knowhow and r i g h t s t o build reforming

furnaces. Both companies we; r rejected (3). Hercules proceeded t o develop i t s
own reforming c a t a l y s t and firrnace, s t a r t i n g up a small plant in1940.
A t the outbreak of N o r l o War

IL, t h e United s t a t e s ammonia industry was ill-equipped

t o handle the quantity of n l t i o g e n required to support the war e f f o r t , since the
major producers of a m o n i a , UuPont a t Belle, kest Virginia and Allied Chemical a t
Hopewell, Virginia were s t i l l ciependent upon coke for hydrogen. There were seven
other plants--a11 qisite s n a l l . Five u w d e l e c t r o l y t i c hydrogen, one cracked refinery
g h s e s and one reforr.ed n a t u r r . 1 gas. Cotisc?quer.tly, the U. S. government had conc t x w t t a terI nt-w aim . l a p L s 1 with a c r s t i a a t e d annual productive capacity of
b O V , C W t o 9OC,OOO to-1s p i j t ' d r of nitrogen--more than twice the productive
c d F a c i t y C J f the p1ail:s ~ I r i r . I , oprratio:: ( 3 ) .
Of the ten new plants L d i l t t.y the Government, s i x were based on steam methane
rcforminL. IC1 loared a t e a r of engineers t o cooperate i n the construction of three
of the refoiming p l a n t s , and undoubtedly the I C 1 knowhow was of influence on the
design of the other three reforming plants.

ICI's i n t e r e s t i n refoiming of' hydrocaibons was not l i m i t e d t o gaseous hydrocarbons,

A S e a r l y a s 1936, I C ] had demonstrated the a b i l i t y t o reform s u l f u r - f r e e d i s t i l l a t e
hydrocarbons. This technique was not commercially applied u n t i l 1954 when a plant
a t Heysham, England was adapted t o reform a s u l f u r - f r e e s y n t h e t i c hydrogenated
gasoline with a 192'C end p o i n t . After development of a s u l f u r removal process, t h i s
p l a n t was converted t o reform s t r a i g h t run d i s t i l l a t e f r a c t i o n s w i t h the same end
point.
The e a r l y naphtha reforming p l a n t s operated a t l o w pressure, but further'development
work led t o a pressure process which permitted r e f u m i n g up t o 400 pounds pressure
a t steam to carbon (mol) r a t i o s comparable t o those used i n steam methane reforming.
The success o f the I C 1 StLam Naphtha Reforming Process is being demonstrated today
P r a c t i c a l l y all ICI's capacity t o produce
DY I C I ' s own construction program.
anmonia and methanol s v n t h e s i s gas is already converted from coke to naphtha reforming. Adaitional annunia p l a n t s based 0x1 naphtha reforeirig a r e planned or under
construct ion.
Furthermore 13 towns gas plants producing a 400-500 Btu per cubic f o o t gas from
naphtha a r e operating or under construction i n Great Britain.
Reforming Reactions
The r e a c t i o n s occurring i n steam naphtha reforming are b a s i c a l l y the same as those
i n steam methane reformfrig, with t h e a d d i t i o n of a s e r i e s of r e a c t i o n s , extremely
complex due t o the length and configuration of the carbon chain of t h e heavy
hydrocarbons making up the naphtha fraction.
The p e r t i n e n t reactions a r e shown i n Table 11. I n r e a c t i o n 1, s u b s t i t u t i o n of
for CnHm y i e l d s a statement of the o v e r a l l r e a c t i o n f o r steam methane
methane ((XI,+)
reforming. In a l l p r o b a b i l i t y the a c t u a l r e a c t i o n mechanism c o n s i s t s of a crackingdehydrogenation r e a c t i o n , which produces carbon, and a concurrent and competing
r e a c t i o n of carbon with steam t o y i e l d hydrogen and the carbon oxides,

In t h e case of a naphtha containing various p a r a f f i n i c , aromatic and naphthenic

compounds having a b o i l i n g range encompassing C4 to C1o f r a c t i o n s , the complexity
of t h e r e a c t i o n mechanism increases g r e a t l y .

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The a b i l i t y of t h e reformipg process t o operate successfully depends upon the
avoidance of carbon laydown. Two mechanism for carbon laydown can-be i d e n t i f i e d :
one based on the equilibrium r e l a t i o n s expressed by-equations (2.1, (3.) and (4;)
in Table XI, and the other based on t h e cracking-hydrogenation-polymerization
r e a c t i o n s of the hydrocarbon.
I n t h e case of the f i r s t mechanism, based on t h e r e a c t i o n of an average l i g h t
d i s t i l l a t e hydrocarbon with steam, IC1 has computed a tendency to form carbon i n
This carbon forming r e a c t i o n takes place very
t h e range-of lo00 t o 1200.P.
r a p i d l y i n the presence of n i c k e l c a t a l y s t . In t h i s temperature range, should the
steam rate be reduced below a c e r t a i n hfniwnn, carbon forms Instantaneously througho u t each c a t a l y s t p e l l e t causing t h e p e l l e t t o d i s i n t e g r a t e . '
The second car& forming mechanfsm is believed t o occur as a r e s u l t of a crackingdehydrogenation r e a c t i o n , followed by polymerization to t a r r y substances which, i n
t u r n , carbonize t o a s o f t sooty carbon. This carbon forma on t h e e x t e r i o r of the
c a t a l y s t not within the i n t e r s e c t i c i e s . No damage t o the c a t a l y s t results from t h i s
carbon deposition. The a c t i v e surface of t h e c a t a l y s t Is blanketed, thereby reducing
i t s a c t i v i t y and a l s o building up pressure drop through the c a t a l y s t bed. This type
of carbon can be removed by oxidation (Le. regeneration with steam and air) without
impairmant of c a t a l y s t a c t i v i t y or physical strength. Prevention of carbon is a
matter of maintaining s u i t a b l e steam r a t i o s and keeping t h e r e a c t a n t s i n contact
v i t h the c a t a l y s t . Care must be exercised in loading t h e c a t a l y s t so t h a t bridging
is avoided.
Reaction 1, in Table I1 is a highly endothermic reaction. Reaction 3, which is t h e
w e l l known water-gas s h i f t r e a c t i o n , is exothermic. This, coupled with the complexity
of the feed a n a l y s i s and t h e p o t e n t i a l f o r carbon deposition, makes necessary the s e l e c t i v e
u r e , o f a c a t a l y s t which promotes the desired reactions while also i n h i b i t i n g the
r e a c t i o n s leading t o carbon deposition. It a l s o n e c e s s i t a t e s p r e c i s e control of t h e
heat input p r o f i l e t o the tubes of t h e reformer.
Refonmd gas from the naphtha reformar c o n s i s t s of hydrogen, carbon dioxide, carbon
monoxide, methane and t r a c e s of heavier gaseous hydrocarbons. Feed naphtha Is
completely converted. The presence of methane i n the gas r e s u l t s from e i t h e r , or
both, t h e i n i t i a l cracking r e a c t i o n of the naphtha o r r e a c t i o n 2 (shown i n Table XI)
which is t h e reverse of the steam methane reforming reaction.

The IC1 Process

The IC1 process c o n s i s t s of s u l f u r removal and steam reforming over a special IC1
c a t a l y s t , followed by conventional processing techniques t o make hydrogen synthesis
gas f o r imrsonia o r methanol and towns gas.
Sulfur removal is fundamental t o the successful performance of t h e IC1 refarming
c a t a l y s t , as the c a t a l y s t is s u l f u r s e n s i t i v e . A three-bed d e s u l f u r i z a t i o n process
i s usually required. The f i r s t bed is a bed of zinc oxide; the second bed a cobalt
molybdate c a t a l y s t ; t h e t h i r d bed another bed of z i n c oxide.
Elemantal s u l f u r and hydrogen s u l f i d e are absorbed by t h e z i n c oxide. Mercaptan
and d i s u l f i d e s u l f u r , in t h e presence of hydrocarbons and z i n c oxide, are converted
to hydrogen s u l f i d e , which it3 then absorbed by the zinc oxide. Thioethers are a l s o
hydrogenated t o hydrogen s u l f i d e and 8fmilarly ramovad. Other s u l f u r compounds are
non-reactive in t h e presence of zinc oxide and are hydrogenated over cobalt molybdate
c a t a l y s t t o hydrogen s u l f i d e , which is removed In the f i n a l zinc oxide bed. The
s u l f u r concentration in the feed to t h e reformer is reduced to between 3 and 5 p a r t s
per o i l l i o n .

44
The zinc s u l f i d e formed i n the above process must be p e r i o d i c a l l y replaced. I n
the case o f naphthas with high s u l f u r content, i t may be economic to use preliminary
e l e c t r o s t a t i c acid treatment to remove most of t h e s u l f u r before the three-bed
treatment.
After d e s u l f u r i z a t i o n , t h e vaporized naphtha passes t o the steam reformer where it
i s admixed with steam and converted to a hydrogen-rich gas. The steam reformer
i s t h e h e a r t of the process. Suspended i n t h e c e n t e r of i t s firebox are vertical
tubes packed with c a t a l y s t . These suspended tubes are heated e x t e r n a l l y by a l a r g e
number of burners. Advancement i n furnace design and tube metallurgy have gone
hand i n hand w i t h advancements i n c a t a l y s t technology. Reformers today n o t only
can reform l i q u i d f r a c t i o n s but a l s o produce a t higher space v e l o c i t i e s , with higher
f l u x d e n s i t i e s and higher tube w a l l temperatures than have been considered f o r
methane reforming.
A simple o u t l i n e drawing o f a t y p i c a l steam reformer is shown i n Figure I.

Desulfurized, vaporized naphtha flows down through a bed of c a t a l y s t contained i n a

multitude o f tubes. Because the r e a c t i o n s occurring a t t h e top of the tube are
highly endothermic, a l a r g e q u a n t i t y of heat must be contributed to the r e a c t i o n t o
prevent carbon laydown. Various furnace designs accomplish t h i s i n d i f f e r e n t ways.
(4) I n the furnace design shown (Selas Corporation of America), the v a r i a b l e heat
input down t h e length of t h e tube is accomplished through t h e u s e of a multiple
number of r a d i a n t cup burners arranged in h o r i z o n t a l rows which can be independently
f i r e d t o give t h e optimum heat p r o f i l e .
The tube w a l l temperatures of a naphtha reformer w i l l operate in the range of 1700
t o 1750'F.
The generally accepted technique f o r manufacture of t h e c a t a l y s t tubes
is permanentmold c e n t r i f u g a l c a s t i n g of a Type 310 s t a i n l e s s s t e e l (ASTM 297-55
The g r a i n formation is such t h a t the tubes have higher stress values than t h e
HK).
extruded tubes.
Despite the g r e a t e r carbon laydown p o t e n t i a l of naphthas relative t o gaseous hydrocarbons, t h e I C 1 c a t a l y s t is a b l e to operate continuously without carbon laydown or .
l o s s of a c t i v i t y , even a t operating conditions more severe than those of conventional
steam methane reforming. Current designs a r e based on a 3 t o 1 steam t o carbon m o l
r a t i o and 400 pounds pressure. O u t l e t temperatures, determined by the desired
Straight-run naphthas with end
e f f l u e n t gas composition, range from 1200 t o 1500.F.
p o i n t s as high as 400F can be reformed. There i s no r e s t r i c t i o n on t h e degree of
aromaticity,
Application Of The I C 1 Process

The a p p l i c a t i o n s of the I C 1 Steam Naphtha Reforming Process are the same as those of
t h e conventional steam methane reforming process. The process produces a hydrogenrich stream containing, as i m p u r i t i e s , carbon dioxide, carbon monoxide, methane and
traces of heavier gaseous hydrocarbons. This stream i s subsequently processed by
conventional techniques t o g i v e e i t h e r a r e l a t i v e l y pure hydrogen, a hydrogen-nitrogen
mixture f o r amnonia synthesis, hydrogen-methane mixture f o r towns gas, or a hydrogencarbon oxide mixture f o r methanol or oxo chemicals manufacture.
Block-flow diagrams are shown i n Figure I1 t o d e l i n e a t e t h e fundamental d i f f e r e n c e s
processing schemes f o r hydrogen, ammonia s y n t h e s i s gas and towns gas manufacture.

Of

The scheme Qr hydrogen generation includes s u l f u r removal, the primary reforming

reaction, s h i f t conversion (where t h e carbon monoxide is reacted with steam to
produce w r e hydrogen and carbon dioxide), and p u r i f i c a t i o n t o remove carbon dioxide
and to methanate the r e s i d u a l q u a n t i t i e s of the carbon oxides back to methane by

i
i

1
1

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r e a c t i o n with hydrogen ( a r e v e r s a l of the reforming reaction). The r e s u l t a n t

f i n a l product has only p a r t s per million of the carbon oxides which are c a t a l y s t
poisons i n most processes t h a t require hydrogen. The reforming operation w i l l be
a t temperatures s u f f i c i e n t l y severe t o minimize t h e methane i n the o u t l e t of the
reforming process. The concentration of methane w i l l usually be of the order of 1
t o 47. depending upon t h e ultimate use of the hydrogen.
The scheme for cumnonia synthesis d i f f e r s from t h e hydrogen generating scheme by t h e
a d d i t i o n of a secondary reformer which combusts p a r t of t h e p o d u c t stream with air.
The secondary reformer introduces t h e nitrogen required t o y i e l d a 3 t o 1 hydrogennitrogen mixture which, a f t e r p u r i f i c a t i o n , goes to an armnonia s y n t h e s i s converter.

It is obviously not necessary t o reform t h e naphtha as severely i n t h i s scheme,

since a c e r t a i n amount of r e s i d u a l hydrocarbon can be used t o combust with air.
Under t h e less severe operating conditions, t h e methane content i n t h e product from
t h e reformer w i l l be i n the range of 7 t o 10%. It is i n t e r e s t i n g t o note t h a t , even
i n cases where the reforming is not done under severe conditions, naphtha does not
show up i n the product from t h e reforming step.
I n t h e secondary reformer, a f t e r combustion, t h e gases pass through a c a t a l y s t bed
t h a t f u r t h e r reduces the methane content. The secondary reformer is a refractorylined vessel which operates a t a temperature higher than t h e o u t l e t temperature of
t h e primary reformer, thereby making it possible t o achieve concentrations of methane
i n the product a s low a s one-quarter of one percent.
The balance of the processing s t e p s are s i m i l a r t o hydrogen manufacture, i.e.
conversion and p u r i f i c a t i o n .

shift

I n the production of towns gas, t h e process scheme v a r i e s g r e a t l y with the f i n a l

s p e c i f i c a t i o n s of t h e towns gas. I n p r i n i c p l e however, as shown i n Figure 11, a
low-severity reforming and s h i f t conversion s t e p is required. Addition of an
enrichment gas is a l s o required, and some balance must be s t r u c k between carbon
dioxide removal and i n e r t gas makeup.
Naphtha Reforminn Vs. Steam Reforminq
A t t h e present t i m e , t h e determinent f o r using Naphtha Reforming i n s t e a d of Steam
Reforming i s more one of raw m a t e r i a l a v a i l a b i l i t y than one of economics. I n major
market a r e a s of t h e world, n a t u r a l gas e i t h e r does not occur o r has not been d i s covered and developed. In these a r e a s n a t u r a l gas can only be made a v a i l a b l e by
l i q u i f i c a t i o n and tanker shipment. The economies of these a r e a s are therefore
oriented around o i l s f o r h e a t i n g and, t o an ever decreasing e x t e n t , around coal,
Naphthas are usually i n long supply, as t h e gasoline consumption i s n o t g r e a t
enough t o absorb them. Here the I C 1 Steam Naphtha Reforming process has its
broadest application.
On the other hand i n an econamy b u i l t around n a t u r a l gas a s a f u e l , and with a l a r g e

automobile population a s is the case i n the United S t a t e s , naphthas as a raw material

f o r reforming are too expensive r e l a t i v e t o n a t u r a l gas.

To demonstrate the r e l a t i v e values of naphtha and n a t u r a l gas as raw materials f o r

reforming d a t a have been developed-from a r e c e n t l y published paper on t h e economics
of reforming ( 5 ) . By comparing t h e r e l a t i v e requirement of feed and f u e l f o r naphtha
reforming and E t h a n e reforming a breakeven curve has been p l o t t e d as s h a m i n
Figure 111.

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I n Great B r i t a i n , which conforme t o t h e condition of an oil-based o r coal-based

economy, lacking n a t u r a l gas r e s o u r c e s , naphthas i n l a r g e q u a n t i t i e s can be
contracted f o r a t a p r i c e of about 0.8 c e n t s per pound. The breakeven value of
n a t u r a l gas i s 47-48 c e n t s per m i l l i o n Btu--not an unusually high p r i c e i n terms
of t h e U. S. economy, but without s i g n i f i c a n c e i n Great B r i t a i n where t h e gas i s
not n a t u r a l l y available.
However, i n t h e case of t h e United S t a t e s which i s the l a r g e s t natural-gas-fuelbased economy having a l a r g e automobile population, naphthas on the East Coast s e l l
in t h e range 1.5 cents per pound. The n a t u r a l gas breakeven is about 90 c e n t s per
m i l l i o n Btu, o r j u s t about double t h e going market p r i c e f o r n a t u r a l gas.
h e United S t a t e s economy, with r e s p e c t t o taoutces and uses of n a t u r a l gas,
automobile population, and r e f i n i n g capacity is a mature enough economy t h a t no
unusual d i s l o c a t i o n of t h i s p r i c e s t r u c t u r e is a n t i c i p a t e d . Such is not the case
i n many of t h e major market areas such as Great Britain. Extensive d i s c o v e r i e s of
n a t u r a l gas in Holland and the North Sea could have a s i g n i f i c a n t bearing on the
f u t u r e economics of t h e e n t i r e European area.

To t h e e x t e n t that n a t u r a l gas replaced f u e l o i l f o r heating purposes, crude o i l

runs would be reduced, t h u s reducing the surplus of naphtha. The expanding
automobile population of Europe would absorb more of the naphthas. h e n e t r e s u l t
would be firming of t h e p r i c e f o r naphtha.
I n view of t h e p q t e a t i a I Q u n s t a b l e f u e l economy in Europe, many naphtha reforming
p r o j e c t s under bid r e q u i r e r a t i n g of the naphtha reforming equipment on n a t u r a l gas.
The I C 1 process i s r e a d i l y converted t o methane reforming.

Basic t o naphtha reforming a r e the following processing s t e p s not required by methane

reforming:

1. Desulfurization. E i t h e r a f i x e d bed o r combination of e l e c t r o s t a t i c acid

t r e a t i n g and a f i x e d bed.
2.

Vaporization f a c i l i t i e s f o r naphtha.

3.

Imperial Chemical I n d u s t r i e s aaptha reforming c a t a l y s t .

4. Larger capacity f a c i l i t i e s f o r carbon dioxide ramoval.

Were a naphtha reforming p l a n t t o be converted t o Prthane r e f o d n g , t h e acid- .
t r e a t i n g s u l f u r removal s t e p and t h e naphtha vaporizer could be dispensed with.
The fixad-bed d e s u l f u r i z e r could be used f o r remaval of s u l f u r from the n a t u r a l gas,
although t h e d e s u l f u r i z e r would be g r o s s l y oversized. The I C 1 c a t a l y s t w i l l reform
metkana equally well as naphtha. Carbon Dioxide r m a l f a c i l i t i e s would be overs i z e d , s i n c e the less favorable carbon-to-hydrogen r a t i o of naphtha, r e l a t i v e t o
methane, r e s u l t i n t h e production of amre carbon dioxide per u n i t of product. (See
Table 111)

In the case of c a p i t a l investment, i t has been s h m ( 5 ) t h a t the b a t t e r y limits cost

f o r an amPonia p l a n t based on naphtha reforming is about 18%g r e a t e r than f o r one
based on methane reforming. For a p l a n t t o produce 97% p u r i t y hydrogen, the naphtha
reforming p l a n t investment i s about 30% g r e a t e r than t h a t of one based on methane
reforming. It should be noted that although the two percentage f i g ~ r e Sare d i f f e r e n t
by a l a r g e degree, n e v e r t h e l e s s t h e order-of-magnitude d i f f e r e n c e s of t h e absolute
v a l u e s are roughly comparable, s i n c e the comonia p l a n t c o s t includes t h e c o s t of the

47

ammonia synthesis loop, Technological advances i n the IC1 process during the past
year have r e s u l t e d i n pressing the technological f r o n t i e r back f a s t e r than methane
reforming, and the spread between the c o s t s f o r naphtha reforming and methane
reforming a r e probably somewhat diminished foday.
Conclusion

Science has demonstrated over the y e a r s the a b i l i t y t o develop new technologies

t o meet t h e ever increasing demands ofpopulation f o r food.
What once was a problem of elimination of s t a r v a t i o n has now become a problem of
maintenance, and improvement, of a minimum d i e t .
Technologies have been developed which f r e e t h e world from the uneconomic r e s t r i c t i o n s
on t h e uae of raw materials t o manufacture f e r t i l i z e r s . DevelopWW of o i l resources,
shipping f a c i l i t f e s and technologies, such a s the Imperial Chemical I n d u s t r i e s Steam
Naphtha Reforming Process, permit the construction of economic f a c i l i t i e s f o r amPonia
manufacture anywhere i n the world.
The problam of carbon deposition when r e f o d g l i q u i d f r a c t i o n s has been solved by
the developlnent of the IC1 c a t a l y s t . Continued development work on naphtha reforming has pushed naphtha reforming techhology beyond methane reforming technology,
and furnaces a r e now being designed a t higher space v e l o c i t i e s , higher pressures,
high tube w a l l temperatures and high h e a t f l u x d e n s i t i e s .

1. "Chemistry i n The Service of Man"-by Alexander Findlay, Longmans, London, 1916

2.

"World F e r t i l i z e r Requirsmants", Colaman, Chemical 6 Runinearinn News,

Decamber 2, 1963, p. 84

3.

"Cartels i n Action", Stocking 6 Watklns, The Twentieth Century Fund, 1946

4. "Steam &thane Reforming For Hydrogen Production", R. J. Kenard, Jr.,

Petroleum, Narch 6 April 1962
5.

" W e Hydrogen by Naphtha Reforming", J. Voogd 6 J. Tielrooy, Hvdrocarbon

Proceesinn 6 Petroleum Refiner, Narch 1963.

48

TABU I
Production of Nitrogen Prom Various Sources Before And After World War I
Thousands of tons of nitronen

1913

iA

473

Chilean N i t r a t e
By Product Nitrogen
Cyanamide Nitrogen
Synthetic Nitrogen

,AI

487
402
98

313
42
24
852

x
2
1159

/'

1.

CnHm

+ nH20

n 00

+ 2n + m

TABLE I1

React ions

82

TABLE IIT
Carbon Dioxide Produced BY Reforminn Reactions
Hydrogen Production

- 97%

Steam Methane Reforming

Steam Naphtha Reforming
Amonla Synthesis Gas Production
Steam Methane. Beforming
Steam Naphtha Reforming

t o n s 0 2 1 W SCP H2
14.51
17.90
t o n s ~ ~ I t &nia
o n

1.22
1.58

Figure I

&aim of Selas Corporation of America Steam Reformer

FIGURE 2

Io

z
W

(3

0
U

-z

>

E
E

a
a

e
Y

Y
Y

0
W
W

z
W

c
W

FIGURE 3

51

Breakeven costs of feed & fuel: naphtha

.

reforming vs. methane reforming

0.1
Naphiha cos1 - cenls

0.8

Der pound

1.2

1.6