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Methanol to propylene MTP - Lurgi's way

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 Methanol To Propylene MTP - Lurgi´s Way

Erdöl Erdgas Kohle, Heft 5/2002, S. 234-237

Methanol To Propylene MTP - Lurgi´s Way

KURZFASSUNG

Erdgas wird ohne Zweifel der bedeutende Einsatzstoff im 21. Jahrhundert sein. Dies ist begründet durch den Umweltschutz,
durch die riesigen Erdgasreserven und die angestrebte Reduktion der Fackelgase.
Technologien der Lurgi Oel · Gas · Chemie d. h. Erdgasreforming mit Sauerstoff, Mega-Methanol Synthese und Umwandlung
von Methanol zu Propylen - bieten einen attraktiven Weg zur Vermarktung von preiswertem Gas. Das Wertprodukt ist
Propylen, das mit dem stark steigenden Bedarf der Folgeprodukte bedeutende Wachstumsraten aufweist.
Auf der Basis kostengünstiger und hochselektiver Lurgi Technologien unter Einsatz erprobter Elemente ergeben sich für die
Umwandlung von Methanol zu Propylen IRR (Internal Rate of Return) Werte zwischen 15 und 30 %. Diese Werte hängen von
dem Methanolpreis und dem Produktwert des Propylens ab.

ABSTRACT

Due to environmental requirements and plentiful gas supply sources including the gas being flared there is no doubt that
natural gas will be a key feedstock in the 21st century.
Lurgi Oel · Gas · Chemie technologies - consisting of oxygen-blown natural gas reforming, MegaMethanol synthesis and
methanol to propylene conversion - provide an attractive way for bringing gas to the market wherever low cost natural gas is
available. The valuable product is propylene and will meet the strong demand growth for propylene derivatives.
Based on cost-effective and highly selective Lurgi technologies using proven elements the internal rate of return is between 15
and 30% for the methanol to propylene conversion depending on the methanol feed price and propylene value.
*Martin Rothaemel, Hans-Dieter Holtmann, Lurgi Oel· Gas·Chemie GmbH, Frankfurt, Germany (E-mail:
-Dieter_Holtmann@lurgi.de">Dr_Hans-Dieter_Holtmann@lurgi.de). Lecture, presented at the DGMK International Conference
»Creating Value from Light Olefins«, Hamburg, October 10-12, 2001.

1 INTRODUCTION

What are the incentives to promote technology development in the conversion of natural gas to valuable products?
- plentiful gas supply sources,
- environmental aspects and regulations, and
- "monetizing" the abundant natural gas reserves in remote areas.
Both economic and environmental benefits from the use of natural gas are the driving forces and will support the continuous
innovation regarding gas-based technologies.
Since Lurgi introduced its new Mega-Methanol process for plants with a production of 5,000 t methanol per day, methanol will
be available at a constant low price in the forseeable future. This development has an enormous impact on downstream
technologies for the conversion of methanol to more valuable products. In this field, the use of methanol as feedstock for the
production of olefins is one of the most promising new applications.
Lurgi's new "Methanol-To-Propylene" (MTP) process presents a simple, cost- effective and highly selective technology,
yielding an excellent value-added product for the utilization of natural gas reserves via syngas and Mega-Methanol.

2 NATURAL GAS - A KEY FEEDSTOCK FOR THE 21ST CENTURY

The total proven gas reserves amount to approx. 140 trillion cubic meters worldwide [1] which translates into a gas reserve- to-
production ratio, i.e. a gas reserve lifetime of 61 years (Figure 1). Furthermore, estimated additional gas reserves will cover a
lifetime of 65 years more. Compared with the reserve lifetime of 41 years for petroleum and 230 years for coal, there is no
doubt that natural gas will be a key fuel component in the 21st century [2].
Among the world regions (Fig. 1), the Middle East and Eastern Europe including the Former Soviet Union (FSU) possess the
largest fraction of global natural reserves with 35% and 38%, respectively [1].
North America and Europe, on the other hand, have gas reserve lifetimes of about 10 years only (Fig. 1), so these regions
soon will be importers for natural gas and gas-based products. Due to the long distance to the gas producing regions, logistics
and technologies of natural gas transport present serious challenges. The situation is complicated because the cost of
transporting gas is high compared to crude oil; hence it will become increasingly important to develop or improve technologies
to convert natural gas to valuable products which can be transported cost-effectively to the markets.
Existing technologies for natural gas conversion are shown in Figure 2: via the conversion to syngas, hydrogen and ammonia,
Fischer-Tropsch products, methanol and DME are produced. Currently, the production of chemicals requires around 5% of
world gas consumption [3].
Lurgi Oel·Gas·Chemie GmbH focuses on a new route from C1 to a valuable product by combining a chain of proprietary Lurgi

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 Methanol To Propylene MTP - Lurgi´s Way

technologies that base on low cost natural gas supply, large scale methanol plants and an exciting new process for the
highly-selective conversion of methanol to propylene.

3 PROPYLENE - AN ATTRACTIVE PRODUCT

The world wide propylene supply/demand amounts to 53.5 million t for 2000 [5].
Polypropylene (PP) is by far the largest and fastest growing of the propylene derivatives, and requires the major fraction of
58% of the total propylene. The increasing substitution of other basic materials such as paper, steel and wood by PP will
induce a further growth in the demand for PP and hence propylene.
Other important propylene derivatives are acrylonitrile (10%), oxo-alcohols (8%), propylene oxide (7%) and cumene (6%). The
predicted growth rates of the capacities for the derivatives are very impressive, i. e.
5.8% for PP(Fig. 3). The average growth rate for propylene itself is estimated to be 5.6% per year by 2004.
How to satisfy this increasing demand for propylene? - Currently, steamcrackers and FCC units supply 66% and 32%,
respectively of propylene fed to petrochemical processes.
However, asFCCunits primarily produce motor gasoline, and steam crackers mainly ethylene, propylene will always remain a
by-product (e. g. 0.04-0.06 t/t of ethylene for steam crackers with ethane feedstock and 0.03- 0.06 t/t, respectively of motor
gasoline and distillates production for FCC units). Current forecasts indicate an annual growth rate of 4.4% for steamcracker
production and 7.2% for FCC units by 2004.
This results in an increasing gap of propylene production that has to be filled by other propylene sources. Lurgi's new MTP
process directly aims to fill that gap.

4 LURGI'S MEGA-METHANOL TECHNOLOGY

The term "Mega-Methanol" refers to plants with a capacity of more than one million metric tons per year. To achieve such a
large capacity in a single-train plant a special process design is required. For this reason Lurgi focused on the most efficient
integration of syngas generation and methanol synthesis into the most economical and reliable technology for the new
generation of future methanol plants [4] (Fig. 4).

4.1 Autothermal reforming

Pure autothermal reforming can be applied for syngas production whenever light natural gases are used as feedstock to the
process.
The desulfurized (and optionally pre-reformed) feedstock is reformed to synthesis gas at about 40 bar using oxygen as the
reforming agent. Even when using pure methane as feedstock to the autothermal reforming, it is necessary to condition the
synthesis gas, as the stoichiometric number, defined as (H2-CO2)/(CO+CO2) on mole basis, is below 2.0. The most economic
way to achieve the required gas composition is a special operation mode of the methanol synthesis with a very high CO
conversion and a suppressed CO2 conversion. The optimum composition is achieved by recycling hydrogen that can be
separated from the purge stream downstream of the methanol synthesis by a membrane unit or pressure swing adsorption
(PSA) unit.

4.2 Combined converter methanol synthesis (inset in Fig. 4).

In this innovative concept the compressed syngas is first used as cooling agent on the tube side of the gas-cooled reactor. In
the downstream water-cooled methanol reactor, the pre-heated gas is converted under nearisothermal conditions while the
heat of reaction is utilized for the production of saturated steam. The partly converted gas is then routed to the shell side of the
gas-cooled reactor where it is converted to methanol in the catalyst bed. Due to the combination of heat exchange (to preheat
the syngas) and reaction, a declining and therefore thermodynamically favourable temperature profile across the catalyst bed
is established in the gas-cooled reactor, thus leading to very high per-pass-conversion. The product gas is then cooled, crude
methanol is condensed, separated and sent to the distillation unit. The gaseous stream is recycled to the reactor loop after
separation of a purge gas stream which, in turn, is routed to the purge gas separation unit where H2 is separated and returned
to the syngas, and thus to the synthesis loop to adjust the proper stoichiometric number (as mentioned above).
The most important advantages of the waterand gas-cooled reactor concept are as follows:
- high syngas conversion efficiency:
at the same overall conversion, the recycle ratio is about half of the ratio in a single-stage, water-cooled reactor;
- high energy efficiency:
in addition to the high-pressure steam generated in the water-cooled reactor, a substantial part of the sensible heat can be
recovered at the gas-cooled reactor outlet;
- low investment costs:
capital cost savings of about 40% for the synthesis loop can be realized due to the omission of a large feedstock preheater,
savings for other equipment due to the lower recycle ratio and by the 50% reduction of catalyst volume in the water-cooled
reactor;
- large single-train capacity:
studies have confirmed that single-train plants with capacities of 5,000 mtpd and above can be built in one reactor train.
To summarize: the advantages of the Mega-Methanol technology make this process ideally suited as part of Lurgi's route
fromC1 via syngas and methanol to propylene.
An environmental sidenote: 100 billion m3 of natural gas are flared or vented annually [1]. That amount would be sufficient for
feeding about 74 Mega-Methanol plants with a capacity of 130 million t/a total.

5 LURGI'S METHANOL TO PROPYLENE (MTP) TECHNOLOGY

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 Methanol To Propylene MTP - Lurgi´s Way

Lurgi's new MTP process is based on an efficient combination of the most suitable reactor system and a very selective and
stable zeolite-based catalyst.

5.1 Reactor concepts

Basically, the methanol-to-olefins reaction can be carried out in both fixed-bed and fluidized-bed reactors.
While for this exothermic reaction the fluidized bed has inherent advantages in terms of excellent heat transfer and superior
temperature control, there are some disadvantages of this reactor type, especially the difficult scale-up procedure and the
stability of the catalyst (attrition, life time). Furthermore, the fluidized-bed catalyst deactivates rapidly which requires continuous
catalyst regeneration. Typically, the regeneration temperatures are higher than at reaction conditions which results in frequent
temperature shock and additional stress on the catalyst particles. Furthermore, the currently available fluid-bed catalysts are
suitable for ethylene-propylene co-production only but not for propylene alone, hence the separation train has to include the
columns and the cold box required for the purification of ethylene.
For catalytic fixed-bed reactors (preferred to operate adiabatically) the temperature control of the methanol conversion is not
as straightforward as for fluid beds. Usually, the addition of steam and distribution of the feed into more than one reactor is
necessary to limit the adiabatic temperature increase in the reactors. However, fixed-bed reactors can be easily scaled up,
have significantly lower investment costs and provide a more uniform residence time of reactants so that product selectivities
can be maximized. Furthermore, a very selective fixed-bed catalyst is commercially manufactured bySüd-Chemie AGand
provides maximum propylene selectivity, has a low coking tendency, a very low propane yield and also limited by-product
formation. This in turn leads to a simplified purification scheme that requires only a reduced cold box system in comparison
with on-spec ethylene production.
Based on the extensive expertise of Lurgi in the field of catalytic fixed-bed reactors and of Süd-Chemie in the field of
high-performance stable zeolites, we opted for the fixed-bed reactor with Süd-Chemie's proprietary catalyst as the basis for
Lurgi's MTP process.

5.2 Lurgi´s MTP process (Fig. 5).

The methanol feed from the Mega-Methanol plant is sent to an adiabatically operated DME (dimethylether) pre-reactor where
methanol is converted to DME and water using a high-activity high-selectivity catalyst achieving nearly thermodynamic
equilibrium.
The methanol/water/DME stream is routed to the firstMTPreactor where also the steam is added. Methanol/DME are
converted to more than 99%, with propylene as the predominant hydrocarbon product. Additional reaction proceeds in the 2nd
and 3rd MTP reactors. The process conditions in the three MTP reactors are chosen to guarantee similar reaction conditions
and maximum overall propylene yield. The product mixture is then cooled and the product gas, organic liquid and water are
separated.
The product gas is compressed and traces of water, CO2 and DME are removed by standard techniques. The cleaned gas is
then further processed yielding chemical-grade propylene with a typical purity of more then 97%. Different olefin-containing
streams are sent back to the main synthesis loop as an additional propylene source. To avoid accumulation of inert materials
in the loop, a small purge is required for light-ends and theC4/C5 cut. Gasoline is produced as a by-product.
Water is recycled to the steam generation for the process; the excess water resulting from the methanol conversion is purged.
Where suitable, this process water can be used for agricultural purposes after appropriate treatment.
The MTP process operates at slightly elevated pressure (1.3-1.6 bara), moderate steam addition (0.5-1.0 kg per kg of
methanol) and low reactor inlet temperatures (400-450°C).
After a cycle of approx. 400-700 hours of operation, the catalyst has to be regenerated by burning the coke with a nitrogen/air
mixture.
The regeneration is carried out at similar temperatures as the reaction itself, hence the catalyst particles do not experience any
unusual temperature stress during the in-situ catalyst regeneration procedure. Furthermore, by applying a nitrogen purge after
the regeneration is finished,there is no possibility of oxygen breakthrough into the MTP synthesis loop which facilitates
reaching the required propylene specification later on in the purification unit.
The simplified overall mass balance is depicted in Figure 6 based on a combined Mega- Methanol / MTPplant. For a feed rate
of 5000 t of methanol per day (1.667 million t/a), approx. 519,000 t of propylene are produced per year. By-products include
fuel gas and LPG as well as liquid gasoline and process water.
A closer look at the overall hydrocarbon product slate of the MTPprocess is provided in Fig. 7: as can be seen, propylene is
the predominant product of the MTP plant with a carbon based yield of more than 70%, while all other components are formed
to a much smaller degree. The amount of coke being produced during normal operation is extremely low. This allows for long
catalyst cycle times until a regeneration becomes necessary.

6 MTP ECONOMICS

The economics have been estimated for a methanol to propylene plant fed by 1.667 million t/a, yielding 519,000 t of propylene.
The feasibility study is based on the following main assumptions:
- total investment cost (TIC) budget: US $ 185 million
- equity: 20%
- depreciation per year: 10%.
The calculated 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 (Fig. 8).
Depending on the site conditions and the natural gas price, Lurgi's Mega-Methanol technology can reduce the production cost
to US $ 80/t of methanol.

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 Methanol To Propylene MTP - Lurgi´s Way

Assuming US $ 380/t of propylene and US $ 90/t of methanol, the IRR will be 15.6%/a, equivalent to a payback period after
start-up of 4.6 years. The internal rate will increase to 28.7% and the payback period decrease to 2.9 years assuming a
methanol price of only US $ 70/t.
For higher propylene price levels, such as US$ 400/t, the IRR figures result very attractive with 32.3%/a at US $ 70/t of
methanol, i. e. 2.6 years payback period.
Future integration and optimization of the total plant complex including syngas, methanol, propylene production and offsites
facilities will further decrease the capital investment and production costs.

7 MTP TECHNOLOGY STATUS

The technological status of MTPin the areas of process and catalyst can be summarized as follows:
The basic process design data were derived from more than 4000 operating hours of a pilot plant at Lurgi's Research and
Development Center. Besides the optimization of reaction conditions also several simulated recycles have been analyzed. The
next step is a larger-scale demonstration unit in order to obtain more data on catalyst life and to demonstrate the process to
potential customers.
The demonstration unit will be started up at the end of 2001. Furthermore, there is an ongoing effort to optimize the flow sheet
for the commercial-scale process.
The catalyst development is completed and the catalyst has been commercially manufactured by the catalyst supplier.

8 CONCLUSIONS

There are abundant natural gas reserves providing low cost feedstock for methanol production and aiming at better use of
natural resources especially in case of associated gases being flared. Propylene produced from methanol will increase the
value of natural gas considerably and offers an exciting potential of growth and a high earnings level.
Lurgi's expertise is well known in designing and building plants to produce synthesis gas from all kind of fossil fuels and
convert the synthesis gas into methanol. The plant record is very impressive. Lurgi's Mega-Methanol technology allows to
reduce the methanol production costs to below US $ 80 per ton, wherever low cost natural gas is available.
This opens up a completely new field for downstream products like propylene.
Based on a simple fixed-bed reactor system, usual processing elements and operating conditions including a commercially
manufactured catalyst, Lurgi's MTP technology will provide an attractive way to "monetize" natural gas.
Driven by the excellent market prospects and additional environmental aspects, Lurgi Oel·Gas·Chemie has developed its own
technology chain starting from natural gas via methanol to propylene, based on the combination of highly efficient concepts at
low investment costs.

REFERENCES

[1] Energy Information Administration (EIA): »International Natural Gas Information«, 14 Feb 2001, National Energy
Information Center (http://www.eia.doe.gov/emeu/international/gas.html).
[2] Ad. R. Punt: Shell's Perspective on the GTM options.
EFI - Gas to Market Conference, San Francisco, October 11-13, 2000.
[3] Th. M. Quigley and Th. H. Fleisch: Technologies for the Gas Economy. EFI - Gas to Market Conference, San Francisco,
October 11-13, 2000.
[4] S. Streb and H. Göhna: Mega-MethanolTM - paving the way for new down-stream industries.
World Methanol Conference, Copenhagen (Denmark), November 8-10, 2000.
[5] St. J. Zinger: Propylene: A Valuation Evaluation.
2001 World Petrochemical Conference, Houston, March 28-29, 2001.
Rothaemel, M.; Holtmann, H.-D.

Quelle: Erdöl Erdgas Kohle, Heft 5/2002, S. 234-237

ISSN: 0179-3187
Dokumentnummer: 200205041

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