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Pergamon Press Ltd.
~) 1983 International Association for Hydrogen Energy.

Int. J. Hydrogen Energy, Vol. 8, No. 4, pp. 285-290, 1983.

Printed in Great Britain.

COST-EFFECTIVE METHODS FOR H Y D R O G E N P R O D U C T I O N

R. G. MINET and K. DESAI
Kinetics Technology International Corporation, Pasadena, California, U.S.A. and
Union Carbide Corporation, Tarrytown, New York, U.S.A.
(Received for publication 5 October 1982)
Abstract--Hydrogen is the key element in the upgrading processes for heavy oils, synthetic fuels, oil shale, tar
sands and unconventional raw materials for liquid fuels preparation. Producing hydrogen in bulk from various
hydrocarbon feedstocks requires serious evaluation of alternate processing routes to determine the most favorable
economic impact on the overall system. This paper discusses several commercially proven systems for large-scale
hydrogen plants including partial oxidation of heavy feedstocks, steam reforming combined with several options
such as wet system processing, Pressure Swing Adsorption, high and low temperature shift, and the influence of
product purity. The comparisons will include process descriptions, operating cost factors and overall efficiency
evaluations.
INTRODUCTION
While hydrogen is one of the most important chemical
materials produced by the process industries, it is seldom the final product sold. Normally, the hydrogen
produced is consumed as an intermediate for various
specialized purposes such as upgrading various hydrocarbons, minerals or natural products, or for the production of chemicals which utilize hydrogen as part of
their manufacturing process.
Some of the major uses for hydrogen are listed in
Table 1 ( A - D ) . As shown in Table 1A, hydrogen is
necessary in petroleum refining for desulfurization,
hydrocracking, isomerization and dealylation, hydrofinishing of lube stocks, stabilization of cracked material
and to avoid gum formation in gasolines, and in several
other refining technologies. Economic petroleum processing requires the production of more and more light
products from heavy feedstocks which contain high
concentrations of metals and sulfur, causing the demand
for hydrogen to grow substantially from year to year.
This demand is expected to grow from 2 billion SCFD
in 1980 to at least 4 billion SCFD by the year 2000 [1].
The petrochemical sector (Table 1B) uses huge quantities of hydrogen for the production of ammonia and
methanol. In addition, hydrogen is a major constituent
of synthesis gas, a mixture of hydrogen and carbon
monoxide which can be converted over catalyst into
various chemical materials including oxo-alcohols and
synthetic fuels. Hydrogen gasification has found widespread application in the conversion of naphtha and
middle distillates into synthetic natural gas and town
gas. Table 1C lists some other potential uses for hydrogen such as processing of coal, oil shale and tar sands
to convert the solid base materials into liquid fuels for
transportation purposes and chemical feedstocks.
Table 1D continues the list of processes making use
of hydrogen including the hydrogen treating of vegetable oil for the production of margarine and soaps,
Hydrogen is used for the direct reduction of metals,
particularly tungsten and copper along with continually
285

developing processes for the direct reduction of iron

ore to product iron by more economic means. All of
these different uses of hydrogen make use of its chemical
property to react with oxides or to substitute a saturated
bond for an olefin, thus leaving behind a complete
hydrocarbon chain or reduced metal.
N O R M A L SIZE R A N G E OF C O M M E R C I A L
H Y D R O G E N PROCESS PLANTS
Commercial hydrogen facilities have been built ranging in size from as small as 10,000 to as large as
300,000,000 standard cubic feet per day. Very small
plants are in use for the direct reduction of various
metals (other than iron) or for the hydrogen treating
of vegetable oils. The larger plants are used for the
production of synthetic ammonia or methanol and in
petroleum refining applications. Huge units are planned
for producing synthetic natural gas and liquid fuels from
coal.
Hydrogen has been finding some limited specialized
use as a direct fuel for transportation. Most of the space
vehicles which have carried satellites into orbit around
the earth and on long probes into the solar system have
used liquid hydrogen as one of the major propellants.
In addition, hydrogen has been proposed as the ideal
fuel of the future for use in automobiles or for public
transportation including transcontinental aircraft. It
seems well suited for such service since it has the highest
energy per pound of any substance when reacting with
air or oxygen. It is abundant, can be produced in a
relatively economic manner, and produces no air pollution. On the other hand, hydrogen requires expensive
storage volume at high compression or extremely low
temperature to squeeze it into suitable containers to
make use of its exceptional properties for transportation. Considerable work has been done on metal
hydrides which alloy hydrogen to be stored as a solid
material and released by the addition of water as
required. Much work remains to be done on these

286

R. G. MINET AND K. DESAI

Table 1. Some major uses for hydrogen
USA 1980 Consumption
MM SCFD

A.

PETROLEUM REFINING AND UPGRADING

1780

Desulfurization
Hydrocracking
Isomerization
Dealkylation
Hydrofinishing
Gum Stabilization

B.

PETROCHEMICAL PRODUCTION

4700

Ammonia
Methanol
Syn Gas (oxo-alcohols)
Cyclohexane

C.

ALTERNATE FUELS

nil

Coal Processing
Oil Shale Processing
Tar Sands Processing

D.

CHEMICALS PROCESSING

500

Treatment of Vegetable Oils

Reduction of Metals (Cu, Fe, W)

Table 2. Commercial processes for production of hydrogen

problems to reach the stage where hydrogen, as a general transportation fuel, can be considered to be economically viable.

Steam Reforming of Light Hydrocarbons.

PURPOSE OF PAPER
Electrolytic Decomposition of Water.
Partial Oxidation of Heavy Hydrocarbons.
Partial Oxidation of Coal.
Byproduct Hydrogen from Electrolytic
Processes (chlorine).
Byproduct Hydrogen from Cataltyic Reforming.

The purpose of this paper is to discuss processes

which are in actual commercial use for the production
of hydrogen. These may be listed as follows:
(A) Steam reforming of light hydrocarbons
(B) Electrolytic decomposition of water at low and high
pressure
(C) Partial oxidation of heavy hydrocarbons with
oxygen or air
(D) Partial oxidation of coal with oxygen or air
(E) By-product hydrogen from electrolytic processes
(chlorine)
(F) By-product hydrogen from catalytic reforming.
While there are several other processes which have
been considered for commercial use, such as the

COST-EFFECTIVE HYDROGEN PRODUCTION

steam-iron process, only those processes which are listed
above are actually utilized to any extent by industry
except in very special cases.

BASIC ENERGY REQUIREMENTS FOR

HYDROGEN PRODUCTION
One way to examine the various processes is to compare the energy required to produce a unit quantity of
hydrogen utilizing each of the different techniques. This
energy can be expressed in BTUs of thermal energy
consumed for the production of a standard cubic foot
of hydrogen which is subsequently delivered at 300 psig.
In addition, the purity of the hydrogen produced will
be considered at a level between 96 and 99.99% to
permit a proper comparison. In special cases, for
example, the production of hydrogen for use in methanol synthesis or in oxo processes, it is obviously not
necessary or desirable to produce hydrogen of such high
purity. However, in such cases the technology involved
is similar to that employed for producing the pure
hydrogen, and corrections can be made to equivalent
hydrogen quantities, thus these technologies fall into
the same pattern.
Table 3 provides a comparison of energy requirements for the production of hydrogen from various
feedstocks including methane, liquified petroleum gas,

light virgin naphtha, No. 2 fuel oil, bunker 'C' heavy

oil and a typical bituminous coal. Also included in the
table with these various carbonaceous raw materials is
water, having been made conductive by the use of an
electrolyte (either acid or alkali). Processes listed
include high temperature steam reforming, partial
oxidation and high pressure electrolysis [2]. The hydrogen product purity ranges from 96 to 99.99%. The
quantity of energy required is given in thousands of
BTU per thousand standard cubic feet of hydrogen
delivered at 300 psig. The total figure includes all energy
consumed in the process.
Another figure of interest given in Table 3 is the 1981
cost of the energy consumed, particularly when comparing the thermal processes with those using electrolysis. A unit of energy in the form of natural gas or No.
2 fuel oil is estimated to cost $5 U.S.D. per million
BTU, while electric power is calculated at a cost of 7
U.S. cents per kWh. The table also includes a very
approximate estimate of capital cost for baseload
100MM SCFD plants. The most attractive approach
remains the high temperature steam reforming of light
hydrocarbons.
The cost of hydrogen produced via the byproduct
route is not included in Table 3. Figures for such systems
are not directly comparable since they depend completely on the way in which processing costs are split
among the various products (chlorine, oxygen, etc.).

Table 3. Basic energy requirements for hydrogen production

Feedstock

Btu/SCF (I)

$/MCF (2)

METHANE

425

2.30

45

HTSR

LPG

440

2.40

48

HTSR

LVN

460

2.90

52

HTSR

NO. 2 FUEL
OIL

500

3.40

60

HTSR

NO. 6 FUEL
OIL

550

4.10

125

P.O.X.

BITUMINOUS
COAL

580

4.35

210

P.O.X.

325
325

7.67
5.00

68
55

H.P.
Future

WATER

287

Investment
SMM

(3)

Process Used (4)

(1) Average energy requirements expressed as BTU/standard cubic foot of pure hydrogen
product.
(2) Cost of production of 1000 standard cubic feet of pure hydrogen in a 100 MM SCFD
plant.
(3) Installed investment cost for a grass roots 100 MM SCFD hydrogen plant. 1981.
(4) HTSR = high temperature steam reforming; P.O.X. = partial oxidation;
H.P. = high pressure electrolysis process; Future = advanced design H.P.

288

R. G. MINET AND K. DESAI

T H E STEAM R E F O R M I N G O F L I G H T
HYDROCARBONS

It is of interest to examine, in more detail, the process

for production of hydrogen utilizing the steam reforming
technique. In Fig. 1 one of several of the basic block
schemes utilized for this well-known and widely used
technology is shown. In principle, the technique is the
same for each of the light hydrocarbon feedstocks. The
raw material can be natural gas, liquified petroleum
gas, light virgin naphtha, or with newly developed technology, No. 2 fuel oil [3]. Liquid feedstock is vaporized
by heat exchange with hot streams generated in the
process, or by using an auxiliary fired heater. The
vaporized and preheated hydrocarbon is then passed
through a suitable catalytic system, such as cobalt/
molybdenum or nickel/molybdenum catalysts to convert
the sulfur-bearing compounds into hydrogen sulfide in
the presence of recycled hydrogen. The hydrogen sulfide is then removed by direct reduction with a bed of
hot zinc oxide:
(1) R S H + H 2 ~ R H + H 2 S
RSR+H2 ~RHR+H2S
(2) H2S 4- ZnO --~ ZnS + H20.
Desulfurized feedstock is mixed with high pressure
steam and further heated. The mixed stream of hydrocarbon, steam and hydrogen is introduced into the
catalyst bed contained inside a system of high alloy
tubes heated by high temperature radiant energy generated by the combustion of fuel in a refractory-lined
chamber. In the course of passing through the reaction
tube, the hydrocarbon materials react with steam to
produce a mixture of hydrogen, carbon monoxide and
carbon dioxide. A certain amount of unconverted methane and uncoverted steam exit with the hot gases leaving
the process system:
(3) C H 4 + H 2 0 ~ H 2 + C O + C O 2
(4) CnHm + H20 ~ H2 + CO + COz.
The above equations are not chemically balanced since
the ratio of hydrogen, carbon monoxide and carbon
dioxide are functions of temperature, pressure, other
operating conditions, catalyst activity etc. It is usual to
employ a steam to carbon ratio of 3/1 or 4/1 to arrive
at a conversion of more than 80% of the hydrocarbon
feedstock to oxides of carbon at the outlet of the catalytic reactor.
A suitable series of heat recovery exchangers are
located in the exit stream leaving the HTSR. The gases
then pass through additional catalytic reactors where
carbon monoxide reacts with the steam present to produce additional hydrogen by the water gas shift reaction.
Normally, two stages of conversion are utilized for this
step, reducing the carbon monoxide content to the level
of approximately 0.4%:
(5) CO + H20 ~ H2 + CO2.
Shifted gas is cooled by heat exchange with incoming
boiling feedwater and in the final condensor. Water

collected from this final condensation is usually returned

to the system via a deaerator. The cold, raw gas is
processed in one of several ways to remove carbon
dioxide and the remaining carbon monoxide and other
impurities to deliver to the battery limits of the plant
the desired purified hydrogen product.

I
HP STEAM

J~

PREHEArE._2

[ DESUtFURIZER ]
b.I
"T
[ HEAT EXCHANGER I

REFORMER I~l

FUEL

TM

I .EAT EXCHANGER r:
T

CONDENSATE

I SHIFT CONVERTER I
~'
CONDENSATE

cootERS

I'

RAW HYDROGEN
Fig. 1. Hydrogen production via steam reforming light hydrocarbon feedstock.

Two specific systems for purifying the gas are considered in this paper, although there are several others
in commercial use (Table 4). One of these systems
utilizes a wet process for removal of carbon dioxide.
Frequently, this is carried out through the use of
monoethanolamines solution which has been suitably
inhibited to minimize corrosion problems in the carbon
dioxide stripping step. Aminegard from Union Carbide
is one such typical system. There are many other chemical solution systems which can be used for the carbon
dioxide removal, some of which operate on the principle
of heating for regeneration, while others operate on the
principle of pressure flash down.
The energy required for these various systems
depends to a considerable extent on the degree of
removal of carbon dioxide which is required. The
residual carbon monoxide and carbon dioxide remains
in the hydrogen steam and is usually converted to methane by a catalytic reaction with hydrogen. Methane
present after the steam reforming step plus that produced by hydrogenation of carbon oxides remains in
the hydrogen product, limiting the attainable purity to
96-98%.
An alternate technology to wet scrubbing is the use
of the Pressure Swing Adsorption (PSA) principle [4].
In this system, the carbon oxides and other impurities
are adsorbed in beds of molecular sieves and activated
carbon. Product hydrogen from the PSA system can be
an extremely pure gas which can be used for a wide
variety of chemical and petrochemical processes to considerable advantage. Water vapor, carbon dioxide, car-

COST-EFFECTIVE HYDROGEN PRODUCTION

289

Table 4. Comparison of hydrogen production costs

PSA
TOTAL INSTALLEDCOST
1980, SMM

CONVENTIONAL

22.5

21.0

FEED PLUS FUEL, MM Btu/Hr

1,020

1,006

COOLING WATER, GPM

5,OO0

9,0OO

ELECTRIC POWER, KW

880

l,lO0

85,000

14,000

5,100

5,034

140

130

(590)

(98)

EXPORT STEAM, LB/HR

(750 psig)
PRODUCTION COST, S/Hr.
Feed Plus Fuel (I)
Other Utilities
Credit for Export Steam (2)
Net Cost

4,650

5,066

Cpaital Charges (3)

900

840

Labor & Maintenance

150

210

5,700

6,116

TOTAL PRODUCTION COST

Cost, $/I,000 SCF H 2

2.30

2.45

Basis: 60 MM SCFD, methane feed and fuel; wet process vs PSA; battery limit plant.
(1) Basis $5.00/MM BTU.
(2) Basis $6.90/M lb.
(3) 32% per year.

bon monoxide and methane adsorbed from the raw cold

synthesis gas, are released by the solid adsorbent upon
reduction of pressure into a purge gas stream which is
suitable for firing in the reformer to generate the heat
required for the processing step. By using multiple
adsorbent vessels which are periodically and automatically switched from adsorption at high pressure to
desorption at low pressure, the production of pure
hydrogen is carried out in a continuous manner. The
overall economics of the two approaches can be judged
by comparing the figures given in Table 4 for a typical
60 MM SCFD hydrogen plant based on methane.
In a given situation, assuming feed and fuel hydrocarbon have the same economic value in terms of cost
per million BTU, it is almost always advantageous to
give serious consideration to the PSA process. For very
large hydrogen plants in the range of 100-200 million

SCFD, there is some advantage with the liquid processing system where it is possible to build these in a
single train. As a general rule, the PSA system requires
parallel trains for capacities above 60 million SCFD
even using the most advanced design of polybed available from Union Carbide.

CONCLUSION
This paper has presented various technologies which
can be considered for the generation of hydrogen from
several raw materials. In today's market, it is unlikely
that the techniques currently used (the steam reforming
of hydrocarbons, and the partial oxidation of heavy
hydrocarbons) will be displaced by other technologies
for many years to come. On the other hand, the promise

290

R. G. MINET AND K. DESAI

of hydrogen as a universal fuel for use in fuel cells for

the generation of electricity, and for use for direct
transportation applications, for large automotive services, trains, and transcontinental aircraft, has so many
advantages that it seems inevitable that the advances
that are required to make such systems economically
viable, safe and universally used will be invented and
brought to successful development within the next
20--30 years.

REFERENCES
1. H. G. Cornell and F. J. Heinzelmann, Hydrocarbon Processing, pp. 85-90 (August 1980).
2. L. J. Nuttall, ACS Symposium Series 116 (1980).
3. R. G. Minet and O. Olesen, ACS Symposium Series 116
(1980).
4. J. Heck and T. Johansen, Process improves large scale
hydrogen production, Hydrocarbon Processing (January
1978).