Studies in Surface Science and Catalysis

J.J. Spivey, E. lglesia and T.H. Fleisch (Editors)

9 2001 Elsevier Science B.V. All rights reserved. 399

Lurgi's Mega-Methanol technology opens the door

for a new era in down-stream applications

Jtirgen Haid* and Ulrich Koss, Lurgi OeloGasoChemie GmbH, Germany

ABSTRACT
Lurgi's Mega-Methanol is a new technology for converting natural gas to methanol at low
cost in big amounts. This gives the opportunity to replace oil consumption by methanol - so to
speak as easy-to-transport liquefied natural gas - in the petrochemical industry as well as in
the energy and fuel industry. Two processes are briefly presented and economically assessed,
one producing propylene from methanol, the other generating hydrogen.

1. INTRODUCTION
Methanol production is a standard outlet for natural gas. Nevertheless, the methanol price
level in the past hindered a possible extension of the usage of methanol. Methanol costs are
mainly dictated by feedstock costs and capital-related charges. On one hand the individual
methanol synthesis process scheme will influence the efficiency of the usage of the gas, on
the other hand the capital-related charges are affected by the economics of plant scale, both
being effective parameters for lowering the price of the methanol product. Here, the Mega-
Methanol technology contributes its share. It permits the construction of highly efficient
single-train plants of at least double the capacity of those implemented until now.
The resulting long-term stable and low methanol prices may pave the way for a wider use of
methanol, both in the energy sector and as a feedstock in the petrochemical sector. In the
energy sector, fuel cell vehicles with on-board hydrogen generation from methanol are ready
to market within the next years. In the chemical sector the route over methanol to olefins is
one of the most promising new applications. Another option with high potential is the
conversion of methanol to hydrogen.

2. THE MEGA-METHANOL CONCEPT

The presented technology has been developed for world-scale methanol plants with capacities
greater than 3000 metric tons per day and combines low environmental impact, cost-
optimized energy efficiency and low investment cost [1]. The process concept consists of
proven and reliable elements, which reduces the risks normally linked to a new technology
nearly to nil.
Synthesis Gas Production: The Synthesis gas production section accounts for about 50% of
the investment costs of a methanol plant. This shows that an optimized design of this section
is essential.
Conventional steam reforming is economically applied to medium sized methanol plants and
the maximum single-train capacity is limited to about 3000 mtpd. Oxygen-blown natural gas

* Author to whom correspondence should be adressed, e-mail: Dr_Juergen_Haid@lurgi.de

400

.n ,,,
.....t
0 ox, o. / I.,o,o:,.;.i !
l
,u..
A'r ~~#~]~.....s:,a:al.l.:.n...I =FuelGas [L..R:c~ Methanol

Fig. 1: Mega-MethanolConcept using AutothermalReforming

reforming, either in combination with steam reforming or as pure autothermal reforming,
nowadays is considered to be the best suited technology [2,3]. Whenever light natural gases
are to be processed, pure autothermal reforming can be applied.
Autothermal Reforming is a low investment process using a simple reactor design. No tubular
steam reformer, till now a sensitive and expensive equipment item of a methanol plant, is
required. The capacity limits for single-train plants are shifted due to the considerably lower
gas volumes. In addition, the autothermal reforming process achieves CO2 and NOx emission
reductions of 30 % and 80 % respectively compared to conventional steam reforming.
The process is a combination of steam reforming and partial oxidation. The chemical
reactions are defined by Eqs. 1-4, assuming that natural gas consists purely of methane.
Combustion reactions: CH 4 + 0 2 = CO + H 2 + H 2 0 (1)

CH4 + 2 0 2 = CO 2 + 2 H 2 0 (2)
Thermal and catalytic reactions: CH 4 + H 2 0 = CO + 3 H 2 (3)

CO+H20 = CO 2 + H 2 (4)
The process produces a carbon-free synthesis gas at reformer outlet temperatures typically in
the range of 950 - 1000 ~ Commercial experience exists for pressures of up to 40 bar. The
synthesis gas is in an equilibrium with respect to the methane reforming reaction (Eq.3) and
the shift reaction (Eq.4). The stoichiometric ratio SR = (H2 - CO2) / ( CO + CO2) below 2.0.
However the optimum stoichiometric ratio SR for the methanol synthesis is between 2.05 and
2.1 and will be achieved by recycling hydrogen that can be separated from the purge gas
downstream of the methanol synthesis by a membrane unit or pressure swing adsorption unit.
The autothermal reactor is a refractory-lined pressure vessel with a burner in the reactor top
section for fast and uniform mixing of the gas/steam mix with oxygen. The combustion and
reaction zone is located above the catalyst bed. The catalyst employed is similar to the steam
reforming catalysts commonly used in tubular reformers (NiAI203). Because of the operating
conditions, establishing a stable flame contour is essential to protect the reactor walls and
catalyst from excessive temperatures. Consequent process optimization throughout fifty years
of experience as well as the help of a proprietary, three-dimensional Computational Fluid
Dynamics (CFD)-model, led to an optimized design of modern Lurgi Autothermal Reformers
with regard to efficiency and availability.
Methanol Synthesis Loop: Efficient syngas-to-methanol conversion is essential for low-cost
methanol production. Based on the well-known water-cooled tubular methanol reactor and on
a new highly active Cu/ZnO catalyst generation [4] a combined converter methanol synthesis
was developed mainly for the application in Mega-Methanol plants. (Fig.2).
 401

The first reaction stage is still a water-

cooled tubular reactor, nearly identical
to the original Lurgi design. However,
here it accomplishes partial conversion
of the syngas at higher space velocities
and higher temperatures. This results in
a significant size reduction of the
reactor compared to the conventional
process while the raising steam is
available at a higher pressure (--50 bar).
The effluent of this water-cooled
reactor is directly routed to a second Fig. 2: Combined convertermethanol synthesis
reaction stage, a gas-cooled reactor.
The cooling medium, passed through the empty tubes of this second reactor, is cold feed gas,
designated for the first reactor. It is routed in countercurrent flow to the effluent from the first
reactor which passes through the catalyst bed outside the tubes. Thus, the temperature of the
reacting gas outside the tubes is
continuously reduced while passing 300 ,- ~ ,~ , ,

through the catalyst bed. By this,

throughout the whole catalyst bed the
equilibrium driving force for the
methanol synthesis reaction is
maintained (Fig.3).
0 ! ,

0 02 0.4 0.6 0~8 1

The combined converter methanol Catalyst height
synthesis is characterized by single-
pass conversion above 80%. Thus the
6 Reaction
<> Cooling gas ,
i
I
recycle ratio can be reduced by 50% Fig. 3: Temperature Profile Gas-Cooled Reactor
compared to the recycle ratio in a
common single-stage, water-cooled reactor.
As fresh synthesis gas is exclusively fed to the first stage, no catalyst poisons enter the second
stage which result in a virtually unlimited catalyst service life for the gas-cooled reactor. In
addition, two-stage reaction control also prolongs the service life of the catalyst in the water-
cooled reactor. If the methanol yield in the water-cooled stage decreases as a result of
subsiding catalyst activity, the temperature in the inlet section of the gas-cooled reactor will
rise with a resulting improvement in the reaction kinetics and hence, an increased yield in the
second reactor stage.
A 50 % reduction of catalyst volume for the water-cooled reactor, the omission of a large
feedstock pre-heater and savings for other equipment due to the lower recycle ratio translate
into capital cost savings of about 40 % for the synthesis loop.
Economies of Mega-Methanol: As already mentioned, feedstock costs and capital-related
charges are the major parameters for the production costs. Table 1 illustrates the feedstock
consumption, the capital invest and the resulting production costs for a conventional steam
reforming plant and Mega-Methanol plant. The results show that the high efficiency of the
process and the low investment costs of a Mega-Methanol plant permit a reduction of the
methanol costs to only 80 US$/mt at gate.
 403

olefins conversion, the process stands out with its high selectivity, simplicity and low
investment required.
The simplified overall mass balance is depicted in Figure 4 based on a combined Mega-
Methanol/MTP plant. For a feed rate of 5000 metric tons of methanol per day (1,667 million
metric tons annually), approx. 519,000 metric tons of propylene are produced annually.

Fig. 4: MTP process route and production figures

The basic process design data were derived from more than 4000 operating hours of a pilot
plant at Lurgi's R&D Center. A larger-scale demonstration unit in order to obtain more data
on catalyst life and to demonstrate the process to potential customers is expected to go on-line
in the summer of 2001.
Based on today's economical conditions, a stand-alone MTP project could yield an internal
rate of return of more than 20 % provided that low-cost methanol is available. Integrating this
concept with a Mega-Methanol plant is a logical consequence. Fig. 5 gives an impression of
the economics of the MTP route, in which methanol is a mere intermediate.

35 The feasibility study is based on the

following main assumptions:
"..g30
lg 25 9 Total investmentcost (TIC) budget:
'3 20 185 million US$
0
380 $~tPropylen'~ ~ 9 Equity: 20 %
11~15
m
eL--~ l O 9 Depreciationper year: 10 %
' I
0
e- 5

0
,i i
60 70 80 90 100 110
F Methanol Feed, $1mt

The results concerning internal rates of return (IRR) on total capital employed depend on the
methanol feed price and the propylene product price that can be obtained. Different propylene
price levels have been considered. Yielding an attractive IRR already at moderate propylene
prices, the combination of Lurgi's Mega-Methanol and MTP technology closes the gap from
natural gas to propylene.
404

Methanol to Hydrogen (MTH): Methanol to Hydrogen is a well-known and proven

technology that has been applied in more than 50 plants world-wide. All these plants are of
capacities smaller than 2.000 m3N/h. At the same time more than 100 naphtha based hydrogen
plants are operated in India, China and Japan. Their total capacity is equivalent to about 5
million mtpa of methanol. Substituting this naphtha by methanol produced from natural gas
can be another challenge.
A,
In the Lurgi MTH plant a methanol / Methanol

water mixture is converted on a copper

based catalyst at low temperatures (250
Water
- 300~ and medium pressure ( 2 5 - 30
bar) into hydrogen, carbon monoxide
and carbon dioxide. After cooling the Hydrogen
product, the remaining gas impurities are PSA Unit
removed by Pressure Swing Adsorption
(PSA). Fig. 6: Flow scheme of a Methanol to Hydrogen plant

Presently, the constraint for the implementation of MTH is the supply with low-cost
methanol, but in principle this technology can be scaled up easily to huge capacities, because
only standard equipment is used.
MTH Steam Reforming of Naphtha
Feedstock price US$ 80 per mt US$148 per mt
Feedstock demand 60.3 t/h 35.0 t/h
Investment costs US$ 33 million US$ 46.5 million
H2 production costs US$ 543 per mt US$ 552 per mt

Table 2: Comparison of Key Operating Data

Comparing MTH with conventional steam reforming for a 100 000 m3N/h Hydrogen plant,
indicates that methanol can compete against naphtha as feedstock to the steam reforming
process. Price stability of the methanol feedstock in comparison to a naphtha feed here also
can be considered an additional big "pro" of this route.

4. CONCLUSION
The low methanol price linked to the Mega-Methanol technology gives an option to replace
the consumption of oil by natural gas in wide areas of the petrochemical industry. Easy to
ship, methanol solves the problem of utilization of natural gas resources located in remote
areas. MTP and MTH are only two among other technologies forming the nucleus for future
developments. Altogether, these technologies will bring the owners of gas reserves in a
position to convert their resources into products creating the maximum value-added.

REFERENCES
1. H. G6hna, "Concepts of modern methanol plants", World Methanol Conference, Tampa (USA) December
8-10, 1997
2. "Low cost routes to higher methanol capacity", Nitrogen, 224, November/December 1996
3. T.T. Christensen and I.I. Primdahl, "Improve Syngas Production using Autothermal Reforming",
Hydrocarbon Processing, March 1994
4. N. Ringer, "The importance of reliable catalyst performance for mega-methanol plants ", World M,.~hanoJ
Conference, Copenhagen (Denmark) November ~ ;:i', 2-9~v: