Ind. Eng. Chem. Res.

2005, 44, 5073-5078 5073

What Will Come after Petroleum?

Octave Levenspiel†
Chemical Engineering Department, Oregon State University, Corvallis, Oregon 97331-2703

The 20th century saw the use of petroleum dominate the process industries and with it came
the birth and growth of chemical engineering and chemical technology. We now are beginning
to realize that the world’s petroleum reserves are not infinite. Because they are rapaciously
being consumed, their costs are rising, and the time will come when we will have to look for a
replacement for petroleum. Considering the world’s insatiable appetite for petroleum, the only
reasonable large-scale source will have to be coal. There are three distinct paths from coal to its
first product, syngas, the starting point for much of the organic chemicals industry and for the
production of liquid fuels. In this first step, 60+ giant corporations have in the past all explored
just one of these three paths. The other two paths were practically ignored. In this paper, I
would like to see if it would be worthwhile at this time to explore the other two paths and to
discuss their possible advantages.

The chemical industry is one that lives or dies by its
ability to introduce new technology and new products,
and the mission of the chemical engineer is to come up
with the processes to make these materials wanted by
man.
There are two steps to what we do: first we conceive
or dream up what we consider to be the best scheme,
and then we try to make it become a reality. The second
step, transforming the idea into reality, is what concerns
us chemical engineers most of the time, and we are very
good at this. However, what about the first step, the
dreaming up of a process scheme? Usually there are
many different paths to the product. How do we choose
the very best scheme? Who does this choosing, and how
does the doer go about doing this? Can this be taught,
and if so, how is it taught today, and who teaches it?
David Royston, referring to this first step in the
development of a process, said,1 “I liken this phase as
being on top of a hill looking over a landscape of
opportunities. You must make best use of the views.
Once you set off down one of the many paths to your
objective it becomes increasingly difficult to turn back
and try another path. Your momentum to the chosen
objective is almost impossible to overcome”.
It is this first step that I would like to address here.
To learn how to choose among alternatives is largely
ignored in the educational world. Why? Maybe we
educators consider it to be unteachable, or else maybe
we do not know how to teach it. Whatever the reason,
we may be able to gain insight into how to do this by
actually trying to do it ourselves. For this, let me select
an example, probably the most important group of
processes today, those which produce a mixture of
hydrogen and carbon monoxide, called synthesis gas or
syngas, from coal.
Why Syngas Is So Important?
There is active discussion today about what should
be the main source of fossil energy that our societies
Table 1. U.S. Department of Energy Estimate of the
Country’s and World’s Fuel Reserves3
liquids,
petroleum natural gas solids, coal
U.S. 186 Q 220 6980
World 5775 5137 30100 Q
use? We can use either natural gas, liquid petroleum,
or solid coal, shale, or tar sands as the starting point
for energy production and for the preparation of organic
compounds.
Savropoulos,2 the forward-looking chairman of Dow
Chemical Co., the largest U.S. chemical company,
recommends that the U.S. switch the fuel at electric
utility power plants from natural gas to oil. Others have
other recommendations. However, the Department of
Energy’s recent report3 shows fossil energy resources
(in Quads, or Q ) 1015 Btu) distributed as shown in
Table 1. These data show that the U.S. has roughly 30
times as much coal as it has liquid or gaseous reserves.
So, in the long run we should look to our coal reserves
as the source for fossil energy and for the production of
organic chemicals. Unfortunately, today most societies
are carelessly squandering their cheap, easy to get
petroleum and natural gas reserves to fuel their econo-
mies. However, things will change because these re-
serves will not last too long.
South Africa has much coal but no petroleum re-
serves. Knowing that petroleum will become in-
creasingly scarce and expensive in the not too distant
future, they took the long view and decided to use coal
as the basis for producing syngas and synthetic fuels.
As an illustration, the reactions for producing gasoline
are
gasification Fischer-Tropsch reaction
coal + steam 98 CO + H2 98
syngas
CnH2n+2
gasoline

† To whom correspondence should be addressed. Tel.: (541) Syngas is also the starting material for a whole host of
753-9248(home).Fax: (541)737-4600.E-mail: levenspo@peak.org. organic materials, as shown in Figure 1.
10.1021/ie040169b CCC: $30.25 © 2005 American Chemical Society
Published on Web 02/05/2005
5074 Ind. Eng. Chem. Res., Vol. 44, No. 14, 2005
Figure 1. Some of the many uses of syngas.
Table 2. Requirements for an Ideal Syngas Process
1 only use air, steam, and coal
2 no N2 leaves with the product gas
3 no O2 plant to be used
4 no tar or liquid to be formed
5 all entering and leaving flow streams are close to
ambient conditions
6 process must be simple, practical, and easy to operate
Syngas from Coal
We produce syngas by two reactions:
coal + steam f CO + H2 + ... + Q + ... (1)
coal + air f CO2 + N2 + ... - 3Q + ... (2)
The first reaction produces what we want; the second
reaction provides the heat needed to make the first
reaction go. In considering this operation, we spot a
number of potential problems:
(i) If coal is reacted with both air and steam in one
reactor, then nitrogen is present in the product stream
and is costly to remove.
(ii) If we try to avoid this problem by using oxygen
instead of air, then we would need a source of pure
oxygen, again costly.
(iii) We can avoid the nitrogen separation problem by
running the two reactions in different locations, but then
we have the problem of transferring heat from one
location to the other.
(iv) Also, in all of these schemes, if the product gas is
rapidly cooled, then tar forms, and this is also costly to
remove. To avoid this, we must keep the product gases
hot for a while to let the tars crack into lower molecular
weight compounds.
Table 2 shows what we would like to have in an ideal
syngas process.
Three Major Routes to Syngas
Basically there are three distinct routes for making
syngas from coal; see Figure 2:
Route 1. Run both reactions in one reactor and then
separate the wanted from the unwanted products.
Route 2. Run the two reactions in separate reactors
and transfer heat from one to the other.
Figure 2. Three routes to syngas.
Figure 3. Two classes of Route 1 processes: (a) N2 removed before
gasification; (b) N2 removed after gasification.
Route 3. In a hot unit, run the desired reaction
endothermically until the reactor cools; then in the same
unit, switch the feed to the heat-generating reaction
until the reactor heats up. Repeat this procedure.
Route 1 to Syngas
It is interesting that over 60 organizations4 have
developed all sorts of contacting schemes to explore
route 1. These processes fall into one of two types. Some
first remove nitrogen from air and then introduce pure
oxygen into the reactor. Others use air directly and then
remove nitrogen from the product gas; see Figure 3 and
Chart 1.
The cost of the units needed to separate the waste
gases, especially nitrogen, from syngas is high. For
example, Sasol Corp. has chosen to use the scheme of
Figure 3a, which uses pure oxygen. To produce this,
they recently reported5 that they were inaugurating
their 15th oxygen separation plant at a cost of $100
million! In fact, Sasol Corp. is the world’s largest single
producer and consumer of oxygen, using not 30 or 300
tons, but over 30 000 tons of oxygen per day, most of it
just to make syngas! In fact, all of these 60+ operations
of Figure 3 are quite complex and quite different from
one another. This is shown in the examples of Figure
4.
Let Us Look at the Possibility of Using Route 2
All 60+ attempts to date to make syngas took route
1. No one has attempted route 2. So let us ask, why not
try to run these two reactions, eqs 1 and 2, in separate
units? There is no need for multimillion-dollar oxygen
plants or other equipment to separate the waste materi-
als (N2, CO2, etc.) from the wanted (CO, H2, etc.). Just
transfer the heat from unit to unit. It would be so much
simpler and cheaper than separating materials.

Chart 1. Coal Gasification Concepts
What held back the development of this type of
system was the problem of transferring heat from the
combustor to the gasifier. However, the relatively recent
invention of the heat pipe came into the picture in the
mid-1960s to make this route look feasible and worth
exploring.
Use of Heat Pipes
The heat pipe is a crafty and efficient device for
transporting heat from a hot place to a cold place. It
consists of a sealed pipe with a wick going from end to
end and containing just the right fluid, which depends
on the temperature range being considered. At the hot
end (the evaporator), the vapor pressure is high so the
liquid boils. At the cold end, the vapor pressure is low
so the vapor flows to that end and condenses. Then by
capillarity the condensed liquid is drawn along the wick
from the cold end back to the hot end.
If the heat pipe is vertical with the cold end above,
then gravity aids the downflow of the liquid. As an
illustration, Figure 5 shows a horizontal heat pipe and
a more efficient vertical pipe, which has the hot end
below and the cold end above.
The heat conductance of the heat pipe is very, very
large, and it is slowly being adopted by the chemical
industry. To illustrate its action, consider a water heat
Ind. Eng. Chem. Res., Vol. 44, No. 14, 2005 5075
pipe. If the hot end is at 100 °C (1 bar) and the cold end
at 81 °C (0.5 bar), the vapor would flow from end to end
at sonic velocity and then condense. This represents an
enormously large heat flow rate. So, in general, by
choosing the correct fluid, we can operate heat pipes at
temperatures anywhere from below room temperature
up to 1000 °C and beyond. Also, by using a whole forest
of heat pipes, we should be able to develop a counter-
or cocurrent heat exchanger, as shown in Figure 6.
For this type of syngas operation, the gas-to-solid
volume ratio, from stoichiometry, is very large, as is
shown in Figure 6. This means that by using finely
powdered coal the flowing mixtures are just slightly
dusty gas, and plugging of the vessel by solids should
not be a problem. There are a host of additional
unanswered questions with this concept. How would one
clean this unit? How about start-up and shutdown?
Should the two reacting streams be run countercur-
rently or cocurrently? What about possible tar buildup?
Certainly these questions should be looked into. In any
case, this contacting scheme should not be dismissed
offhand.
Heat pipes are especially efficient because they use
the latent heat of the carrier fluid to transport heat from
the combustor to the gasifier. However, because of the
high temperatures involved, choosing a suitable carrier
fluid and finding suitable materials for construction of
the heat pipes may be difficult. However, it should be
looked into.
Route 2 Alternative
Instead of relying on the latent heat of a carrier fluid
to transport heat, we may more simply just circulate a
fluid, which is heated and cooled as it circulates between
the reactor and gasifier. Figure 7 shows two variations
of this concept. Detailed process calculations will tell
which approach is preferred.
Route 3 Periodic Operations, the REGAS
Process
There is another whole class of operations that have
been bypassed by the 60+ developers in the past. Out
of curiosity, let us look at this group of operations. Who
knows, maybe we can get something useful from it?
Reactor-Gasifier (REGAS) Process
Chemical engineers embrace continuous processes,
and they avoid cyclic processes whenever possible.
However, here is a situation where cyclic processes could
possibly be used advantageously.
Consider a long vertical vessel containing an inert
ordered packing or brickwork that will not settle when
the temperature is widely cycled. This vessel will be
used to run reactions 1 and 2, one after the other. As a
simple illustration, for a constant volumetric feed rate
of feed gases, let us take the vessel through an operating
cycle of combustion and gasification, in, say, 8 h.
t ) 0-5 h. In this first step of the cycle, the vessel is
fed from below by a very lean (but stoichiometric)
mixture of fine coal powder suspended in air (1 volume
of coal to at least 24 000 volumes of air). The coal burns
and heats the bed solids, a sharp hot front slowly rises
up the vessel, and the packing behind the front is all
heated.
At 5 h, all of the bed solids are hot. So, turn off the
coal-air mixture and introduce the coal-steam mixture
(1 volume of coal to at least 5000 volumes of steam).
5076 Ind. Eng. Chem. Res., Vol. 44, No. 14, 2005
Figure 4. Some complex designs of the route 1 processes from ref 6.
Figure 5. Horizontal and the more efficient vertical heat pipes.
t ) 5-8 h. Gasification occurs, CO and H2 (syngas)
forms, and a cold front rises up the bed such that at 8
h the whole bed is cold, as it initially was at t ) 0.
This cycle is then repeated.
In the ideal case, which we illustrate here, we assume
that these rising hot and cold fronts will be sharp.
However, even with the same volumetric flow rates of
feed gases, these fronts will not rise at the same rate.
From the heats absorbed (reaction 1) and released
(reaction 2) and from the fact that the combustion gas
consists of 80% inerts, in an 8 h cycle it will take 5 h to
heat the bed solids and 3 h to cool them. Figure 8 shows
the condition of such a tower at hourly intervals.
Compare REGAS with the Ideal Process
First let us compare this scheme with the ideal
process of Table 2:
(i) In the combustion step (t ) 0-5 h), only air, not
oxygen, is used. Hence, there is no need for nitrogen
removal either before or after the gasification step. In
addition, there is no need for an oxygen separation
plant.

Figure 6. Heat pipe exchanger-gasifier, or the EXGAS concept.
Figure 7. Countercurrent and cocurrent circulating carrier fluid
exchanger-gasifier, or the EXGAS concept.
(ii) Because fresh syngas has to pass through the hot
bed (see Figure 8), any tar formed at the heat front will
hopefully be destroyed. Also, the volumetric gas-to-solid
ratio, x, that we must pass through the vessel, from
Figure 8. One cycle of operation of the REGAS process, showing the time of rise of the hot and cold fronts.
Ind. Eng. Chem. Res., Vol. 44, No. 14, 2005 5077
stoichiometry, is as follows:
for air at 1 bar at 200 °C x ) 24 000
at 1000 °C x ) 65 000
for steam at 1 bar at 200 °C x ) 5000
at 1000 °C x ) 13 000
In actual operations where an excess of gaseous
reactants may be used, these ratios could be larger still.
With such gas-to-solid ratios, the mixtures are very,
very lean and slightly dusty gases. Would such a unit
plug with ash? I wonder.
(iii) In the ideal case, the hot and cold heat fronts are
assumed to be sharp, but in the real case, S-shaped heat
fronts will form, caused by the axial dispersion of
flowing gases and by the unsteady-state heating and
cooling of the packing material. This leads to thermal
inefficiencies, which can be estimated from long heat-
regenerator theory.7,8
(iv) As for the leaving flow streams, we would like
them to be at close to ambient conditions. However,
Figure 8 shows that in 3 h of the 8-h cycle the exit
stream leaves hot. This is not the very best. However,
with a change in the feed direction during the gasifica-
tion step, one can keep the hot front within the vessel
for most of the 3 h period.
(v) How long would a cycle take? Minutes? Hours?
Longer? Actually, preliminary estimates by Dudukovic
and Levenspiel9 suggest that a 60-m-high regenerator
should be able to operate on an 8-h cycle.
(vi) Finally, with the slowly advancing heat fronts,
the process should be simple, easy to control, and
practical.
The above discussion shows that REGAS has, in large
part, met all six requirements of the ideal syngas
process of Table 2.
5078 Ind. Eng. Chem. Res., Vol. 44, No. 14, 2005
There are all sorts of other things to look into with
the REGAS process such as flow velocities changing
with temperature during a cycle, sulfur removal, com-
mon to all syngas processes, etc. However, these prob-
lems all represent the second step in the development
of a project. As mentioned earlier, this is something we
chemical engineers are good at, and it is not what this
paper is about.
REGAS and the Old Water Gas (or Blue Gas)
Process
The REGAS process does not resemble any of the 60+
processes reported in ref 4. However, it appears to have
some similarity with the old water gas (or blue gas)
generator of the early 1900s, in which a batch of coke
is charged into a spherical or squat dome-shaped vessel,
heated to red heat by combustion with air, and then
contacted with steam to produce the desired gas. The
key difference between these processes can be sum-
marized as follows:
(i) In the water gas generator, coke is used as the
reactant, packing material, and heat storage medium.
In the REGAS process, inert solids are used for packing
and for heat storage.
(ii) Coke is charged batchwise in the water gas
generator, and powdered coal is fed continuously in the
REGAS process.
(iii) The flow pattern approaches mixed flow in the
water gas generator, with the whole batch of solids
heating or cooling at the same time, while plug-flow and
moving heat fronts are aimed for in the REGAS process.
This fact is responsible for the low thermal efficiency
in the former process and the expected high efficiency
in the REGAS process.
(iv) There are many possible extensions and improve-
ments to the basic REGAS presented here. For example,
if the direction of the feed flow is reversed after every
cycle, this would help flush out any trapped solids from
the bed.
Such an extension can be explored as one looks
further into this matter. However, in this paper I just
want to point out that here is a concept that should be
looked at because it may possibly be used advanta-
geously.
Comments on the EXGAS and REGAS Processes
and the Conclusion
Let us return to David Royston’s analogy of being at
the top of a hill that has three routes down to the
bottom. We would like to find the best route down. Note
that the 65+ previous walkers all took the same route
down, leaving the other two routes overgrown with
weeds and poison oak. Should we just follow the lead of
the previous walkers because they had made it down,
or should we also explore those other two routes?
If I followed the other 65+, I could maybe do as well
as they did but likely no better. However, if I explored
either of the other two routes (which, in principle, look
attractive), I may hit the jackpot. Also it should be
mentioned that this may be one of the most important
industrial reactions of our times. Thus, it may be
worthwhile to explore these alternatives.
In conclusion, a generation ago O. A. Hougen ended
his Bicentennial Lecture on Chemical Engineering
History10 with the following question:
“Would it not be appropriate now for chemical engi-
neers to collaborate in the hydrogenation of coal for the
production of synthetic liquid fuels for motor vehicles
before our supply of petroleum runs out?”
Acknowledgment
I am very grateful to Felipe Lopez-Isunza of UAM
Iztapalapa, to Tom Fitzgerald of greater Los Angeles,
and to Mike Dudukovic of Washington University
for the time they spent on my first draft of this paper,
and I thank them for their useful discussions and
comments.
Literature Cited
(1) Royston, D., personal communication.
(2) Chem. Eng. News 2003, July 7, 7.
(3) Meyer, E. G. Letter to the editor. Chem. Eng. News 2003,
Nov 24, 6.
(4) Nowacki, P., Ed. Coal Gasification Processes; Noyes Data
Corp.: Park Ridge, NJ, 1981.
(5) Chem. Eng. News 2003, Feb 16, 15.
(6) Kunii, D.; Levenspiel, O. Fluidization Engineering, 2nd ed.;
Butterworth: Boston, 1991; p 46.
(7) Levenspiel, O. Design of Long Heat Regenerators. Chem.
Eng. Sci. 1983, 39, 2035.
(8) Levenspiel, O. Engineering Flow and Heat Exchange,
revised ed.; Plenum: New York, 1998; Chapter 15.
(9) Dudukovic, M.; Levenspiel, O. Studies on Coal Gasifi-
cation in Heat Regenerators. Summer exercise, Otter Rock, OR,
1981.
(10) Hougen, O. A. Seven Decades of Chemical Engineering.
Chem. Eng. Prog. 1977, Jan, 89.
Received for review May 24, 2004
Revised manuscript received September 29, 2004
Accepted October 12, 2004
IE040169B