Accepted Manuscript

Title: Energy efficient methanol-to-olefins process

Authors: Alexandre C. Dimian, Costin Sorin Bildea

PII: S0263-8762(17)30612-3
DOI: https://doi.org/10.1016/j.cherd.2017.11.009
Reference: CHERD 2888

To appear in:

Received date: 20-6-2017

Revised date: 1-11-2017
Accepted date: 3-11-2017

Please cite this article as: Dimian, Alexandre C., Bildea, Costin Sorin, Energy
efficient methanol-to-olefins process.Chemical Engineering Research and Design
https://doi.org/10.1016/j.cherd.2017.11.009

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Energy efficient methanol-to-olefins process

Alexandre C. Dimiana, Costin Sorin Bildea

Department of Chemical and Biochemical Engineering, University POLITEHNICA of Bucharest, 1, Gh. Polizu
Street, RO-011061, Bucharest, Romania

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corresponding author a.c.dimian@gmail.com

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Highlights

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 Conceptual design of an innovative energy efficient methanol-to-olefin process


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Reactor effluent energy covers feed preheating, evaporation and superheating
 Mechanical Vapour Compression allows substantial energy saving

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 Reaction heat drives a heat and power cycle integrated with the utility system
 Neutral design as energy requirements and minimum number of units

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Sent to publication to Chemical Engineering Research & Design - 20 June 2017
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Copyright: no publication, no reproduction, no use of any part of content of this paper without
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the written agreement of the authors
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Abstract
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This paper deals with the conceptual design of an energy efficient and cost-effective
methanol-to-olefin (MTO) process. The innovative solution consists in full recovery of the
energy generated by reaction. The reactor effluent enthalpy can cover feed preheating,
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evaporation and superheating in a sequence of three feed-effluent-heat exchanger units. The

novel method employs mechanical vapour compression for upgrading the
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temperature/enthalpy profile of the condensing water/hydrocarbon mixture, recovering a

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considerable amount of energy, otherwise lost by water quenching. Saved energy may pay
back the compressor cost in about one year. The energy released in the reactor is used for
running a combined heat and power cycle. The power is sufficient for driving the
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compressors, while the low-pressure steam may run an ammonia-absorption refrigeration

plant that supplies most of the cold utilities in separations. The olefin separation and
purification is handled in a compact scheme of five columns, energetically integrated with the
reaction and preliminary separation sections. The ethylene/propylene splitter is designed for
high recovery and flexible operation. Heat pump is implemented for propylene purification.
 2

Rigorous sizing is performed for the key units. Operation and capital costs are minimised
since the design is almost neutral regarding energy requirements and employs a minimum
number of units.

Keywords: Methanol-to-olefin process, Process systems engineering, Chemical process

design, Computer-Aided Process Engineering, Energy saving

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Introduction

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Olefins are essential building blocks for the organic synthesis. Today the olefins are

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manufactured almost exclusively from fossil oil and gas resources. Modern technologies, as
methanol-to-olefin (MTO) and methanol-to-propylene (MTP), are available by employing

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renewable raw materials, namely biogas and biomass, as well as coal, which in this way
becomes a clean resource for chemical industries. Today methanol is emerging as the most

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important building block for sustainable chemical industries (Olah et al., 2009; Schmidt &
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Pätzold, 2014).
The availability of low-cost methanol is a requirement for profitable MTO business.
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However, a supply-chain of higher-value end-products, namely speciality polymers, allows
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getting profitable margins even with higher methanol cost, as it is the case in Europe.
The starting point for methanol production is syngas (CO and H2 mixture), in turn available
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from various sources, as natural gas, biogas, biomass, or coal. Figure 1 shows the large
applicability of methanol, which embraces a wide range of chemicals and commodity
polymers, today known for the most part as essential petrochemical products. From a
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strategic viewpoint, the MTO process may contribute to decoupling the olefins from the
petroleum market, allowing countries without hydrocarbon resources to develop an
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independent infrastructure of basic chemicals.

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The presentation of MTO technology may be found in several articles (Pujado & Anderson,
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2004; Chen et al., 2012; Ye et al., 2015; Tian et al., 2015). Conceptual process design is
handled only in a recent paper (Yu & Chien, 2016). Here the energy saving is treated by a
method that takes advantage from the potential of the reactor effluent. However, this is not
fully exploited, as we will demonstrate. Their flowsheet is taken as reference case in our
analysis (see Appendix I). Note that the olefins separation makes use of seven distillation
columns.
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In this paper, we propose a novel approach that results in a highly efficient MTO process,
almost neutral as energy requirements and employing a minimum number of separation units.
In the first place, the energy generated in the chemical reactor is fully recovered for methanol
feed conditioning. The novel method employs Mechanical Vapour Compression (MVC) for
upgrading both the temperature and enthalpy of the reactor effluent. The method is highly
efficient, since the spent mechanical energy helps recovering about ten times more thermal
energy. The considerable amount of heat developed in the reactor is used for running a

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combined heat and power cycle, which supplies utilities, namely for gas compressors and an

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ammonia-refrigeration plant. The olefin separation employs a minimum number of five
columns, integrated with the reaction section, which results in an almost neutral process from

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energy viewpoint.

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This paper deals with the conceptual design of a process for manufacturing ethylene and
propylene from methanol with the nominal capacity of 100 tph methanol. Product
specifications are olefins of polymer grade, with over 99% purity. The location is a harbour
site in Europe. U
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The paper is organised as following. The first section deals with the bases of design, including
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catalysis, thermodynamics, kinetics, and HSE issues. It follows preliminary material balance
and process profitability. Then Process Synthesis is developed, with focus on the key
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innovative aspects compared with previous works. The treatment is split in reaction,
preliminary separation and olefins separation sections. The solution is assessed by computer
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simulation, by paying attention to suitability and accuracy of the thermodynamic methods.

The results are material and heat balances, as well as sizing of key equipment. Rigorous
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methods are employed for designing heat exchangers and distillation columns. The final part
handles Process Integration issues, as combined heat & power, refrigeration, heat-pump
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assisted distillation, thermal coupling and management of utilities. Conclusions highlight the
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novelty aspects and the energetic performance of the proposed design.

Bases of design
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Chemistry and catalysis

The transformation of methanol to olefins (MTO) is a complex catalytic process (Alwahabi &
Froment, 2004; Chen et al., 2012). In the first step methanol dehydrates to dimethyl-ether
(DME) by a reversible reaction, followed by conversion to olefins, as ethylene, propylene,
and butenes. Sub-products are methane, ethane, propane, heavier hydrocarbons and aromatics.
 4

2CH3OH 
2  C H O 
2 C H / C H / C H
-H O -H O
2 6 2 4 3 6 4 8
(1)

The MTO reaction takes place in vapor phase in the presence of a suitable catalyst at 350 to
500 °C, and 2 to 3 bar. Today it is agreed that modified silico-aluminophosphate molecular
sieves SAPO-34 is an efficient industrial catalyst in terms of activity, selectivity and
robustness (Tian et al., 2015). The superiority of SAPO-34 over ZSMS-5 is explained by a

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“cage” structure more favorable for the formation of short-chain olefins, as C2 and C3. The

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most agreed reaction mechanism HCP (hydrocarbon cyclic pool) involves short-life
intermediate aromatic species. The size of interconnection channels controls the selective

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conversion of these intermediates to olefins. Smaller pores and shorter residence times favour

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the ethylene yield, while the opposite is valid for propylene. For more references see the
review paper of Tian et al (2015).
The selectivity of SAPO-34 may reach about 40 % weight in each ethylene and propylene, in

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total 80% from the formed hydrocarbons, while the ethylene to propylene ratio may vary in
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the range 0.75-1.25. About 10% of methanol is converted to butenes. It is remarkable that the
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methanol conversion may be pushed to over 99% with very low or none di-methyl ether
formation (Chen et al., 2005; Tian et al., 2015). The variables for varying the yield in olefins
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are the catalyst type, the operating temperature and the gas space velocity.
Coke formation is a crucial aspect for the reactor technology. The catalyst must be
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periodically regenerated, after 1 to 2 hours of operation. For this reason, the reaction set-up
follows the principle of fluid catalytic cracking (FCC) technology, with the difference that the
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reactor itself is a fluid-bed type instead of a riser. More information about various aspects of
MTO process development can be found in a comprehensive review of Ye et al. (2015).
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Thermodynamics and kinetics

The MTO global reaction is highly exothermal, releasing about 850 kJ/kg-methanol at 500 °C
and selectivity mentioned above. Using a fluid-bed reactor allows an efficient removal of the
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reaction heat.
With respect to chemical equilibrium, the situation is complex. The global reaction seems to
be controlled rather by kinetics than by thermodynamics. The prediction of chemical
equilibrium in Aspen Plus by Gibbs energy minimization at 470 °C and 2 bar leads to only
ethylene and propylene in the approximate molar ratio of 1:3 when the specified products are
 5

methanol, di-methyl ether, ethylene and propylene. The same results are obtained by using
REQUIL model by specifying the stoichiometry. Thus, the catalytic reaction is complex and
controlled rather by kinetic factors, as mentioned above.
The kinetics of MTO reaction was the subject of numerous studies, regarding both detailed
and lumped kinetics. The first category considers many species, some identified
experimentally by sophisticated analytical techniques (Alwahabi & Froment, 2004). The
second category regards directly measurable molecular species. This approach allows the

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design and sizing of a chemical reactor for capital cost evaluation. Among the kinetic studies,

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we mention earlier publications, as by Mihail et al. (1983), Bos et al. (1995), Chen et al.
(2012), Ying et al. (2015), Rostami et al. (2016).

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Physical properties

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The list of components involved in the process design comprises methanol, water, light
alkanes and light olefins. Figure 2 shows the normal boiling points of key hydrocarbons.

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These spread-off over 200 °C range. Accordingly, the pressures and temperatures in the
separation operations should be optimised in relation with available utilities. Figure 2 displays
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the vapour pressure against temperature for the key components. The separation of
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ethylene/ethane is relatively easy, but requires low temperature and high pressure, for
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example -20 °C to 4 °C at 26 bar. On the contrary, the separation of propylene/propane is

very difficult, but it can take place at moderate pressures.
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Health, safety and environment issues

Since methanol is highly toxic and volatile, appropriate measures should be taken to preserve
health and avoid safety hazards. There is a vast industrial experience for manipulating
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methanol, olefins and other hydrocarbons. With respect to environment protection, the CO2
emissions are low since the carbon efficiency of converting methanol to hydrocarbon is high
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(over 90%). The only drawback is the formation of a large amount of water, which should
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penalise the economics, but not the environment. Clean water may find valuable applications,
as industrial utility, or agricultural usage.
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Preliminary material balance

Figure 3 presents the Input / Output structure of a MTO process. Inputs are methanol,
catalyst, and air for catalyst regeneration. Outputs are light olefins ethylene and propylene,
 6

heavier olefins and hydrocarbon, LPG fuel including propane fraction, gaseous emissions and
solid waste resulting from catalyst regeneration, as well as water resulting from reaction.

Table 2 presents data for determining a preliminary material balance. The analysis is focused
on process synthesis issues, namely on methanol valorisation, and disregards the catalyst
consumption. However, this may be easily included considering the data presented for the

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reactor design. Note that here the yield is formulated as kg of product for 100 kg total

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hydrocarbons obtained. The data are typical for UOP/Hydro (Chen et al., 2014) and DMTO
(Tien et al. 2015) processes. Note that the methanol conversion is close to 1. It may be

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observed that the amount of methanol required is proportional with (32/14)×w, in which w is

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the weight-fraction of olefin, since one mole methanol results in one mole of =CH2, the
building group of olefin species. The formation of coke and flue gases has been included in a
factor of 5 %w with respect to methanol converted to hydrocarbons. On this basis, one can

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determine the amount of required methanol, in this case 227.81 kg for 100 kg hydrocarbons,
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or 239.20 kg including coke and gases. It results that the weight ratio MeOH to light olefins
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(ethylene plus propylene) is about 3. Note that the reaction supplies 127.81 kg water per 100
kg hydrocarbon, which is roughly 1.6 the weight of light olefins. Since the specific
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consumption is substantial, the methanol cost should be low enough for getting a competitive
process. However, in terms of the carbon conversion to olefins the MTO process efficiency is
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high, over 90%.

MTO process generates very low emissions, above all CO2 by coke combustion at catalyst
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regeneration, while NOx and H2S are absent. If examined over the whole manufacturing
chain, most of CO2 comes from the syngas manufacturing step. From this viewpoint, olefins
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production by MTO process develops significantly less CO2 than by naphtha steam cracking,
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and is fully sustainable even when starting from coal (Chen et al., 2005).
Figure 3 presents the Input / Output material balance for a methanol feedstock of 100 t/h, or
2400 t/day, or 800 ktpy by 8000 hours operation time. The yield data are retrieved from Table
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2. By using a scale factor of 100000/239.2=418.41 the methanol input is converted in

hydrocarbon outputs. The output olefins production is about 304 ktpy, from which 134 ktpy
ethylene, 134 ktpy propylene and 36 ktpy butenes. The propylene to ethylene ratio may be
pushed up to 2.1, since usually there is a larger propylene demand (Chen et al., 2005).
 7

Supplementary production can be obtained by recycling butene and C5+ hydrocarbon to a

separate FCC reactor.

Preliminary economic assessment

A preliminary economic analysis is done in the conditions of Western Europe. The methanol
price is 250 $/t, while for the ethylene, propylene, butene and fuel hydrocarbon the prices are

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1300, 1200, 900 and 500 $/t respectively. We assume the catalyst cost 5% with respect to

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feedstock. A crude estimation of the process profitability can be obtained by calculating the
index rate of return on fixed capital ROIC:

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𝑵𝑷 𝑺
𝑹𝑶𝑰𝑪 = (1)
𝑺 𝑭𝑪

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In the above relation, NP is the net profit before taxes (revenue - all expenses), S the value of
sales and FC the fixed capital. Assuming the turnover ratio S/Fc about 1 for commodity

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industries, the ROI calculation turns into determining the ratio net profit to sales, where the
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net profit is obtained by subtracting from sales the cost of raw materials including feedstock
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(MeOH) and catalyst (Cat), as well as fixed (FC) and variable (VC) costs:
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NP=(S-FC-VC) – (MeOH+Cat) (3)

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Typically for commodity industries (FC+VC) is 30% from sales. In this case, the sales are
368×106 $, while expenses with raw materials and catalyst 210×106 $. It results NP = 111×106
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$ and ROI = 30.1%. This value predicts the possibility of getting a good profitability.
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Process Synthesis
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The process synthesis follows the methodology outlined in Dimian et al. (2014). The results
presented in the next sections have been obtained by employing the process simulator Aspen
Plus version 9.0.
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Reactor-Separation-Recycle structure
Since good selectivity can be achieved at over 99% conversion, there is no methanol recycle.
Figure 4 presents the process block diagram, with three sections: reaction, preliminary
separation, and olefins separation. The reactor is the source of an important amount of energy
 8

that could be used for generating power and heat. The reactor effluent has a high energetic
potential that should be valorised too. The I/O material balance highlights the formation of a
large amount of water, which should be separated before submitting the hydrocarbon stream
to olefins separation. There are also some internal recycles of water for gas quenching and
cleaning. After suitable treatment, the preliminary separation makes available a large amount
of clean water. The dried and impurity-free hydrocarbon stream is submitted to the olefins
separation. This section supplies ethylene and propylene, butenes and C5+ hydrocarbon by-

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products, as well as fuel-type fractions, methane and LPG. More olefins can be produced by

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recycling butenes and C5+ hydrocarbons to a FCC reactor. This method is applied in the
recent DMTO processes (Tian et al., 2015).

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Reactor design
The catalytic reaction is highly exothermic and needs periodic catalyst regeneration. For these

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reasons, the fluid bed reactor appears more suitable than a multi-tubular fixed bed reactor.
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However, adiabatic fixed bed reactors operating with reaction and regeneration cycles are
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employed in the methanol to propylene (MTP) technology developed by Lurgi, (Schmidt &
Pätzold, 2014). The fluid bed reactor may be designed for several gas/solid contacting
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regimes, as bubbling, turbulent and fast fluidized bed (Levenspiel, 1999). Each regime may
lead to quite different conversion and selectivity patterns.
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Currently, the MTO technology is offered mainly by two companies, UOP/Hydro (Chen et al.,
2005) and Chinese Dalian Institute of Chemical Physics, as DMTO technology (Tian et al.,
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2015). Figure 5 presents the reaction set-up used in the DMTO demo plant. Fluid bed
turbulent regime ensures short residence time, reduced entrained solids, and vigorous mass
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and heat transfer. The catalyst is extracted through a tubing system and sent for regeneration
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by coke combustion. The regenerator is of fluid bed type too, this time operated in bubbling
regime. Note that in both reactors the catalyst circulates slowly downwards in counter-current
with the gas. Cyclones and filters are placed in the disengagement space in view of ensuring a
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virtually complete removal of solid particles, including capturing fines below 5 µm. The
industrial SAPO catalyst should be attrition resistant. Tian et al. (2015) also present an
impressive photo of a reactor of 11 meter diameter, built and operating in China. The catalyst
inventory is 45000 kg, handling up to 5500 t/day throughput. The catalyst is removed
 9

periodically, after 1 to 2 hours, for regeneration. Coke deposit around 8 % with respect to
catalyst would favour high selectivity to olefins.
In view of a narrow control of temperature, internals for heat removal may be inserted in the
fluid bed reactor (Avidan et al., 1985; Wei et al., 2014). The cooling device is usually an
assembly of tubes or coils raising HP steam. This should be designed such that the optimal
hydrodynamic pattern is preserved. Further heat recovery may be obtained by cooling the hot
solid catalyst, by employing special heat exchangers. This possibility is neglected in this

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study. However, we highlight the advantage of taking profit from the heat developed in the

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reaction space, namely for driving a combined heat and power cycle that can ensure a
substantial amount of process utilities.

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The design of a large-scale fluid-bed reactor is a complex matter. CFD modelling combined

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with chemical reaction engineering modelling was recently used (Lu et al., 2016). It was
found that CSTR model gives only qualitative results. The transient behaviour of coke
formation and finer description of the hydrodynamics and heat transfer is necessary for

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improving the model accuracy. In practice, several scale-up stages were necessary for
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building-up a robust industrial reaction system (Tian et al., 2015). For the scope of the present
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research, a reactor sizing based on kinetics is not necessary. However, an order-of-magnitude
can be obtained by shortcut calculation. For example, assuming the WHSV of 5 h-1 gives that
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handling 100000 kg/h methanol requires an inventory of 20000 kg catalyst. The gas density at
the inlet is 0.89 kg/m3. Assuming gas velocity 1.5 m/s and residence time 2.5 seconds gives
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reaction volume of 77.7 m3 with 5.136 m diameter and 3.75 m height.

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Table 4 presents the composition of the reactor-outlet mixture that will serve for the
assessment of separations. The flowrates of species have been slightly modified with respect
to Table 3 to account better for the separation of methane, ethane, propane and heavier
hydrocarbons from olefins.

Separation system

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Preliminary separation

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After reaction, a first objective is separating the olefin-rich gas from the large amount of
water, in which methanol and other organic impurities are also soluble. The effluent leaving at

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elevated temperature captures a large amount of energy that could be used for feed preheating.

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An evaluation of this opportunity can be obtained by an analysis of the enthalpy flows around
the reactor. Figure 6 left-hand shows the cumulative enthalpy flow for feed conditioning (cold
curve) and effluent cooling (hot curve). The first incorporates preheating from 25 °C to

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bubble point (segment AB), evaporation at 93.9 °C (BC) and superheating to the inlet reactor
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temperature at 350 ° C (CD), all at 2.5 bar. The second considers de-superheating from 470
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°C to dew-point 109.6 °C (segment FG), where water condensation starts, and further to 70
°C (GH), where gas/ water separation may take place, all at 1.8 bar. The temperature-enthalpy
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curves are obtained by using Hcurve capability in Aspen Plus. The reference value is set to
zero at 25 °C for the cold streams and at 70 °C for the hot stream, at the mentioned pressures.
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The total enthalpy variation for cold stream feed is 48.0 MW, from which about 6 MW for
preheating, 29 MW for evaporation, and 13 MW for superheating. The total enthalpy
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variation for the hot stream is 58 MW, from which 23 MW by de-superheating, and 35 MW
by water condensation. It results that the energy of the hot effluent may cover the energy
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needed by the cold affluent, if suitable temperature driving force is available. Accordingly,
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feed superheating may be covered by the hot effluent on the gas region, while feed pre-
heating and evaporation could be ensured by the two-phase condensation region. The
feasibility of heat recovery can be examined by applying the pinch technology method
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(Dimian et al., 2014). We assume a minimum approach temperature ΔTmin of 10 °C. Match
opportunities may be visualized by shifting the cold curve to the right, for example by
assuming quench with water with a duty of 4 MW. In Figure 6 the segment line ABCD shifts
to A´B´C´D´. Recovering heat from the reactor effluent for superheating the methanol vapour
inflow is possible by using a feed-effluent heat exchanger (FEHE). However, this is not
 11

possible for pre-heating and evaporating of methanol, since the temperature difference
between the hot and cold curves drops below ΔTmin, and eventually the two curves cross each
other. Moreover, the design of the evaporator should manage two very different heat transfer
zones on the hot side, gas phase cooling and two-phase condensation. However, if the hot
curve is lifted sufficiently on the condensation zone GH, matching FEHE heat exchangers for
both methanol pre-heating and evaporation become feasible. This operation should take place
by compressing the vapour phase slightly before reaching the dew point G. The above

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qualitative analysis inspired the novel solution in view of energy recovery, as outlined next.

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The computer simulation with implementation of heat exchangers consolidates these findings.

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Figure 7 presents the flowsheet for reaction and preliminary separation, with key values for
temperatures, pressures and duties. The flowsheet configuration and the parameters of heat
exchangers are optimised in view of energy integration with the olefins’ separation. Methanol

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feed of 100000 kg/h at 25 °C is pumped at 2.6 bar, preheated and evaporated at 89.4 °C
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followed by superheating to 350 °C in a series of three FEHE units, HX-1, HX-2, and HX-3, in
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counter-current with the reactor effluent. The vapour stream enters the reactor R-1, described
by a black-box yield model. The reaction takes place at 470 °C and 2.3 bar. Table 4 shows
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typical outlet flowrate and composition suitable for the assessment of separations. We
consider the methanol conversion of 99 %, although in the industrial practice this is typically
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about 99.9% (Tian et al, 2015). The reactor effluent is quenched to 420 °C to prevent products
degradation, by injecting 4000 kg/h cold water. Then the gas enters the unit HX-3 for
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methanol superheating, where the temperature drops to 211°C. The gas is cooled further to
150 °C in the unit HX-4, in which useful LP steam utility is generated. Note that the heat of
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HX-4 cooler could be directly used in the reboiler of some distillation column. However, this
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heat is small (3.6 MW, compared to 42.4MW recovered in HX-2 and HX-3). Moreover, this
heat integration is likely to make the control of distillation columns more difficult.
In the quench unit QCH-2 an amount of 4500 kg/h water of 85 °C is added, such to condense
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some water vapour from the reactor effluent and reduce the temperature to 106 °C, just below
the dew point. This unit has also the role of gas cleaning by removing in the water stream
organic impurities and escaped catalyst fines, compulsory before entering gas compression.
The waste water stream is sent to treatment, while the gas/vapour stream goes to compression.
 12

Further the gas pressure rises from 1.7 to 2.8 bar by the compressor unit C-1. The temperature
raises by about 50 °C from 106 to 155 °C (point K), while the dew point moves to 125 °C
(point G’). The condensation zone can drive now the units HX-2 and HX-1. This approach
may be described as upgrading the heat recovery potential by Mechanical Vapour
Compression (MVC). Axial or centrifugal compressors are suitable. The fluid consisting of
water vapour and hydrocarbons should not raise corrosion problems. A hard-mechanical
constraint is fulfilled, which limits the outlet gas temperature to maximum 220 °C (Ludwig’s

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handbook, 2001). Note that the energy for compression can be obtained from the energy

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developed by reaction by a combined heat and power cycle, as later outlined. In this way, 29
MW representing the duty of the evaporator HX-2 can be saved by spending 3 MW

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mechanical energy, recovered from the energy developed by reaction by a heat and power

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cycle.
After compression, the gas phase enters the tubular space of the FEHE units HX-2 and HX-1.
In view of designing these units, it is noteworthy to observe that high heat transfer

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coefficients on the hot side can be achieved by creating a turbulent two-phase flow with
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simultaneous water condensation. The rigorous design of these heat exchangers will be
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discussed in a later section.
For exothermic reactions, the positive feedback arising from feed-effluent heat exchange can
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lead to state multiplicity and instability (Bildea and Dimian, 1998). However, the system can
be quite easily stabilized if an appropriate manipulated variable is available for temperature
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control. In the proposed design, the reactor cooling duty is quite large (-15MW). This is
achieved by rising steam, which is very efficient from heat transfer viewpoint and therefore
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should be effective for temperature control purposes. A furnace heater can be provided for
start-up purposes or for controlling the reactor-inlet temperature. Moreover, as the reaction
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mixture containing about 55% water, start-up and temperature control can also be achieved by
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injecting super-heated steam of appropriate temperature.

After pre-heating the methanol, the mixture is cooled by the heat exchanger HX-5 to about 86
°C, and separated in gas and liquid water in the flash QCH-3. After further cooling through
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the exchanger HX-6, deeper water condensation and complete methanol removal takes place
by absorption with chilled water of 5 °C in the column ABS-1. The resulting top gas recovers
over 99.9% of the hydrocarbon species. Other purification steps, not present in the Figure 7,
should be considered. Traces of CO and CO2, harmful for ethylene and propylene
specifications, should be removed by caustic washing. Then the gas stream is submitted to
 13

dewatering and drying. Finally, acetylene removal by hydrogenation might be considered,

located typically after the first olefin compression stage.

The proposed flowsheet may be rated against another separation scheme proposed in a UOP
patent (Miller & Semetar, 2002) and evaluated by simulation (Yu & Chien, 2016), as
described in Appendix 1. The gas effluent is treated by two-step quench cooling, with
intermediate heat recovery for feed pre-heating and superheating. When compared to our

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approach, the key difference is that a large part of the enthalpy of the hot effluent is not

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recovered, but lost in the cooling water. Note that the evaporator needs more heat than the
pre-heater and super-heater together. Importing utility steam represents a double loss of

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energy, for heating and cooling. Following the scheme in Appendix 1, the energy for water

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condensation and cooling is 4.6 MW for QT1 and 24 MW for QT2, in total 28.4 MW,
practically equal with the heat injected in evaporator in our scheme.
A quick economic comparison of two alternatives can be done in term of costs for saving

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thermal energy versus installing a compressor. Assuming 8 $/GJ for LP steam and 8000 h
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annual operation time gives the cost of steam for feed evaporation of
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8×28.8×8000×3600/1000 =6.635×106 $. Considering cooling water at 2 $/GJ gives a
supplementary cost of 1.635×106 $. Thus, by heat recovery the first alternative can bring an
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annual saving of about 8.27×106 $. On the other hand, a raw estimation of the compressor
cost can be obtained by means of the correlation C = a + bSn, in which a = 580000, b =
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20000, S is the power in kW, and resulting cost in USD (Towler & Sinnott, 2013). For 4 MW
power, the compressor purchased cost is 3.5×106 $. Considering an installation factor of 2.5
PT

gives a total cost of 8.7×106 $. Thus, the payback time is about one year. Note that the energy
for compression can be covered completely by the heat available from reaction, by raising HP
E

steam and employing a combined power and heat cycle, as later developed in this paper.
CC

Thus, the advantage of upgrading the heat exchange capacity of the reactor effluent by
compression is demonstrated.
A

Olefins separation section

For the assessment of olefins’ separation section, we consider the mixture given in
 14

Table 4, at 2 bar and 25 °C. The process synthesis makes use of a task oriented methodology
(Dimian et al., 2014). The characteristic property is the vapour pressure of components. Table
1 presents the normal boiling points, while Figure 2 shows the vapour pressure versus
temperature. These data indicate that higher pressure in columns is preferable, since it allows
using cheaper cooling utilities in condensers. On the other hand, lower pressure favours the
phase equilibrium. Thus, the pressure in separations will be an optimisation variable between
equipment and operation costs.

T
The most expensive utility is low temperature refrigeration. We consider a multilevel setup

IP
working with propane (R1270) and ethane (R170). The temperature of propane chillers can be
set between -42 °C (1.013 bar) and 30 °C (10.9 bar), while of ethane chillers between -89 °C

R
(1.013 bar) and -30 °C (10.7 bar). Note also that brines can be used as secondary chilling

SC
agent between the refrigeration station and the process location. Suitable brines are water
solutions with calcium chloride (-37 °C), methanol (-35 °C), ethylene glycol (-20 °C), and
Dowtherm (-70 °C). Property data for refrigerants can be found in Perry’s handbook (2007).

U
The fulfilment of product specifications is a central aspect in the design of separators.
N
Chemical grade purity for ethylene and propylene should be better than 94%, while
A
polymerisation grade purity should be over 99%. Regarding individual impurities that may
affect catalyst activity or product quality, the requirements are very severe for sulphur
M

compounds (1 ppm), acetylene (2 ppm), water (2 ppm), oxygen (5 ppm), CO and CO2 (5-10
ppm), methanol (5-10 ppm). The presence of other olefins is limited to 10 to 20 ppm.
ED

Saturated hydrocarbons, including methane, are tolerated below 1000 ppm (Ullman’s Polymer
and Plastics, 2016). In this project, the purity target is 99.5% polymerisation grade ethylene
PT

and 99.2 % polymerisation grade propylene.

E
CC

Figure 8 presents the flowsheet for olefin separation. This has been simulated with Aspen Plus
9.0. The process starts with the compression section. Suitable pressures for each separation
can be estimated by means of Figure 2. Firstly, the pressure raises at 10 bar by means of two-
A

stage compressor CP-1. By deep cooling at -15 °C, about 50% of the hydrocarbon C3+
separates as liquid. Then the pressure of the remaining mixture is raised by the compressor
CP-2 at 20 bar, followed again by partial liquid separation at -15 °C, such that 50% from the
incoming gas is liquefied. In the last compression level CP-3, after pressure increase at 32 bar
the gas is cooled at -20 °C and separated in gas and liquid streams. At the end, all gas and
 15

liquid streams generated by compression are sent to the first split. By examining Table 5 it
may be seen that multistage compression with intermediate liquid separation contributes to
significant energy saving.
We apply heuristics for split generation and sequencing (Dimian et al, 2014). Firstly, methane
should be removed in the split C-1 as undesirable light impurity. All the output streams from
the compression stage are sent to this stripping column, at suitable locations. To avoid very
low top temperature, a small amount of ethylene (2.3 %) leaves in the vapour distillate. Since

T
C2 and C3 fractions are in equal proportions, 50/50 heuristic applies for the next split C-2.

IP
Ethylene-rich fraction separates in top, letting propylene and heavier components in bottom.
The separation should ensure high recovery of both C2 and C3 hydrocarbons; otherwise the

R
olefin purity specifications mentioned before cannot be fulfilled. In addition, the column

SC
design should allow flexibility with respect to propylene/ethylene ratio in the range 0.75-1.25.
The split C-3 deals with the ethylene purification as ethylene/ethane binary. The split C-4
handles the propylene purification, leaving C3+ components in bottoms. Note that a heat pump

U
is employed for saving energy, as explained later. Finally, the split C-5 separates propane and
N
butenes from C5+ heavies. As result, the above scheme involves five distillation columns,
A
which is a minimum of units for separating a six-component mixture.
In another alternative, the separation scheme could start with a first C2/C3 split, followed by
M

methane removal. The two alternatives are equivalent in terms of capital and energy costs.
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Process simulation issues

Ideal model with Wilson option for activity coefficients and Henry components for
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supercritical species was used in the low-pressure separation section. This ensures an
adequate description of solubility in water of both methanol and hydrocarbons. IAPWS-95
E

method is used for calculating water and steam properties. A cubic equation of state (EOS) is
CC

the choice for higher-pressure olefin separation. The reliability of simulation depends on the
quality of model parameters. This aspect is critical for the design of the propane/propylene
splitter, where the relative volatility is below 1.1. Let us consider a binary mixture of 17000
A

kg/h propylene and 1000 kg/h propane in a column of 150 theoretical stages, at top pressure
of 10 bar and total pressure drop of 1.5 bar. Two thermodynamic models are compared,
Soave-Redlich-Kwong (SRK) and Peng-Robinson (PR), using binary interaction coefficients
available in Aspen 9.0 database. Both models are highly recommended for hydrocarbon
mixtures, with comparable results in many cases. However, here the simulation reveals a
 16

surprise. The reflux ratio necessary for achieving the propylene purity target of 99.5% is 10.1
for PR and only 6.7 for SRK. A difference of 33.6 %! Note that when checking the
condenser duty, the differences in enthalpy of vaporisation calculated by PR and SRK
methods are small and close to the data reported in the Table 2-249 from Perry’s handbook
(2007). Thus, we decided to review the data regression. The search in the Aspen Plus database
of VLE data close to the investigated range (10-12 bar) found recent data by Ho et al. (2006).
The regression with PR and SRK models gives kij values of 0.007348 and 0.001689,

T
respectively. Although the standard deviation is small in both cases, the consistency test failed

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for the PR model. These parameters lead to reflux ratios of 9.88 for PR and 6.2 for SRK.
Since the quality of regression using SRK model seems better, we take the decision to adopt

R
this method for both ethylene and propylene purification columns. The simulation of the

SC
flowsheets presented so far raise no convergence problems.

Sizing
U
Aspen Plus offers interactive sizing for some operational units, as compressors, heat
N
exchangers and distillation columns. The results are briefly presented in this section, as well
A
as in the supplementary material.
Gas compressors
M

Table 5 presents the key characteristics of the compressors, including mass flow, pressure
interval, number of stages and isentropic power. The largest compressor CP-1 (a) is installed
ED

in the preliminary separation section. Then a series of three compressors is employed in the
olefin separation section for raising the pressure of the hydrocarbon stream to 32 bar. One
PT

may see that the intermediate separation of heavier components contributes to save
substantially the needed power. The first compression step CP-1 (b) needs 2.41 MW, while
E

the next steps only 0.38 and 0.13 MW, respectively. Further raise to 32 bar of liquid fractions
CC

pressure is done by simple pumping. In total, the power demand for compression is about 6
MW as isentropic mode, or 8 MW for 75% overall efficiency. Note that 6 MW shaft power is
available by converting 15 MW energy from reaction in a combined heat & power cycle, as
A

shown in Appendix II.

Heat exchangers
In shortcut calculation, an overall heat transfer coefficient U is assumed considering
recommended values for the partial heat transfer coefficient (HTC) on each side. The sizing of
 17

heat exchangers by shortcut methods is presented in the Supplementary Material. Rigorous

calculation can be performed with computer-aided design tools available in Aspen Plus 9.0
known as EDR (Exchanger Design and Rating) procedure. EDR makes use of methods and
software developed by professional organisations, as HTRI (Heat Transfer Research
Incorporated) and HTFS (Heat Transfer and Fluid Flow Service). The procedure may be
applied in design, rating and simulation mode. The computation starts with the assessment of
physical properties and phase equilibrium of fluids involved in models, as viscosity, density,

T
thermal conductivity, latent heats, etc. It follows the design phase, which sets-up a close-to-

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optimum geometry, including rigorous calculation of partial heat transfer coefficients, the
constraints being min/max fluid velocity and pressure drop. The temperature driving force

R
and heat exchange area is determined by zonal analysis. Oversizing from 5 to 10% is usually

SC
considered. Here the design of units aims to keep low pressure drop, namely on the reactor
effluent side, in view of limiting the energy of compression.
Table 6 presents the sizing of the FEHE units HX-1, HX-2 and HX-3. The geometry respects

U
the TEMA norms. The notations are: Ds and Dt as shell and tube diameters, Lt tube length, Nt
N
number of tubes, At exchange area, U overall heat transfer coefficient, and DP pressure drop.
A
MTD is the mean temperature difference determined by zonal analysis, different from LMTD,
which is the logarithmic mean of hot and cold ends. The first row of each unit shows results
M

of shortcut design, to be compared with EDR calculation. It was decided that the hot effluent
should pass through the tubes, since there is a fouling risk, while the methanol should flow
ED

through the shell. The tubes’ diameter is kept constant for the all three units at ID/OD of
28/32 mm. The maximum allowable pressure drop per unit is 0.2 and 0.1 bar for cold and hot
PT

side, respectively.
The HTC computation referring to the cold side is straightforward, since it involves pure
E

methanol that is heated as liquid, evaporated, and superheated as vapour. On the hot side, the
CC

situation is rather complex. The water/hydrocarbon mixture changes from a gas/vapour state,
to water-vapour condensation, and further to convective heat transfer. In the gas/vapour zone
low HTC is expected, but this rises abruptly when water condensation starts at the dew point.
A

The condensation may take place in horizontal or vertical tubes. Highly turbulent pattern may
be achieved by proper selection of the tube diameter and specific flow load. In this case, there
is a large similarity with steam condensation in the presence of non-condensables, for which a
large experimental material is available in the recent years, namely in the field of nuclear
industry (Lee & Kim, 2008). Mean HTC values of about 4000 to 6000, and 8000 to 11000
 18

W/m2K were reported by steam condensation with inert gas in horizontal and vertical tubes,
respectively (Papini & Cammi, 2010). On the two-phase flow zone, HTC values over 1000
W/m2K may be achieved by ensuring highly turbulent non-stratified flow.
The unit HX-1 is of TEMA BEM type, with one pass both through tubes and shell. The EDR
calculation reports HTC values at condensation of 2600 W/m2K, which may be seen
conservative compared with above mentioned research. On the cold side, the HTC for liquid
methanol heating is around 1400 W/m2K. It results an overall clean U of 873 W/m2K. As

T
shown in Table 6, fouling was introduced by means of thermal resistances. These values were
kept constant for the other units. Consequently, the overall U drops at 585 W/m2K, close to

IP
600 W/m2K selected for shortcut design. Note that LMTD and MTD are close.

R
The design of the unit HX-2 can be related with a kettle reboiler following the CKU type. The

SC
mechanism of heat transfer in tubes is described by water-vapour condensation with non-
condensables, except a short de-superheating zone, resulting in HTC over 4000 W/m2K. On
the other side, the methanol evaporates from a pool of boiling liquid, which gives high HTC

U
values. The clean overall U is about 2000 W/m2K, which falls to half when fouling is
N
considered. Note that MTD shows a significant deviation from LMTD, since stiff decay of hot
A
fluid temperature profile at the entry zone.
Finally, the HX-3 unit deals with gas/vapour heat transfer. Good individual HTCs around 200
M

W/m2K are obtained by ensuring high turbulent regime in tubes and shell. However, the fluid
velocity is constraint by the allowable pressure drop. The overall heat transfer coefficient falls
ED

by an order of magnitude, compared with the previous situation, in the range of 100 W/m2K.
Accordingly, HX-3 is a costly unit of 8 shells, with 4 in parallel and 2 in series.
PT

Putting in a nutshell, the EDR calculations indicate that recovering the heat content of the
reactor effluent can be done efficiently in a series of three FEHE units, employing standard
E

shell and tubes heat exchangers, but providing mechanical vapour compression for exploiting
CC

its energetic potential in the water-vapour condensation region.

A

Separation columns
The separation columns in the MTO process deal with absorption and distillation. Table 7
presents key results of sizing. The notations are: NTT and NRT number of theoretical and real
trays, D distillate flow, Dc column diameter, H-tray distance between trays, RR and BR molar
reflux and boilup ratios, Qc and Qr condenser and reboiler duty, Ttop and Tbot temperature of
 19

top and bottom, Ptop and DP, top pressure and column pressure drop. Note that in Aspen Plus
9.0 the design of internals is available in interactive mode. We select trays with an overall
efficiency of 0.75. The location of feed tray(s) refers to theoretical trays. The selection of
pressure in columns is related to the management of refrigeration, as well as by considering
the heat integration with the preliminary separation section. The hydraulic design is organized
by “sections” of constant diameter, in which the trays may be assessed individually. The key
result is the operation point, bounded by min/max liquid and vapour loads, as well as by the

T
tray pressure drop. The target is an operating point around 80% from the flooding point. The

IP
largest columns are C-2, C-3 and C-4, with 38, 78 and 148 theoretical trays, respectively.
Down the feed tray a diameter enlargement is appropriate to accommodate more flow.

R
Accordingly, the columns have diameters of 1.9/2.3, 1.9/2.3 and 3/3.3 m, and are equipped

SC
with high efficiency valve trays Flex-TO. The pressure drop per plate is around 600 Pa. Sieve
and/or Flex-S fast valve trays may be used for the other columns. Reducing the height of
towers may be obtained by diminishing the inter-trays distance from 0.6 to 0.5 or even 0.4 m.

U
The hydraulic bottleneck of this measure can be compensated by slightly larger tower
N
diameter.
A

Process Integration issues

M

Combined heat and power

The high exothermicity of the MTO chemistry offers good opportunities for saving energy.
ED

Maximum 22.6 MW is available with the methanol feed at 470 °C. Colder feed or steam
injection may be used to moderate the reaction exothermicity. This aspect regards the reactor
PT

engineering practice, which is hardly available for this process. On the contrary, it is well
known that heat transfer devices are currently employed for running highly exothermic
E

reactions (Kobayashi et al., 2014). In this project, we select reactor feeding with vapour
CC

methanol at 350 °C, in accordance with the base case study. By feeding at lower temperature
the amount of energy to be removed from the reactor drops from the maximum 22.6 MW to
15 MW. Supplementary energy at elevated temperature is available from flue gases obtained
A

by coke combustion. The potential of this energy is at best exploited by generating HP steam
for producing both electricity and LP steam. This aspect is tackled by the simulation of a
Rankine cycle presented in Appendix II. The cycle may supply about 14 MW LP steam and 6
MW power.
 20

Refrigeration system
Table 8 presents the refrigeration needs in the MTO process. The major part involves the
olefins separation section, including refrigeration of condensers and inter-stage compressor
cooling. In total, the energy of cold sinks is about 20 MW, but this amount is spread at
different temperature levels.
The largest amount of 10.7 MW is required for driving the condensers of C2/C3 splitter C-2
and ethylene purification C-3. The top temperatures are of about -20 °C. Considering 10 K

T
difference leads to -30 °C target for the chilling fluid. A standard two-stage propane cycle is

IP
suitable (Green & Perry, 2007). For safety reasons, the refrigeration is done indirectly by
employing brines, as glycol or CaCl2 solution. The condenser duty of de-methaniser C-1 is 2.5

R
MW. Deeper cooling at -75 °C may be obtained by a cascade of propane-ethane. By assuming

SC
an overall COP factor of 2.0, defined as refrigeration capacity to input energy, gives a
compression power of 6.65 MW.
The energy for gas compression may be reduced significantly, approximately divided by 20,

U
by employing ammonia-absorption refrigeration (AAR) method. Instead of gas compression,
N
the ammonia refrigerant is transported as water solution between low-pressure and high-
A
pressure zones, such that only liquid pumping is needed (Dimian et al., 2014). Thermal
energy of various origins may be used, including waste and solar energy. An important
M

advantage of AAR is large flexibility to demand, in terms of chilling temperature (-50 to +3

°C). Refrigeration capacities from 0.2 MW up to several megawatts are available. Building-up
ED

highly efficient systems of combined heat and power with refrigeration is possible. This is the
case of the MTO process, where abundant amounts of hot water are available at temperature
PT

between 70 to 120 °C, as well as LP steam and flue gases. A disadvantage of AAR is low
COP value, in general from 0.8 down to 0.4, depending on the temperature of the cooling
E

water in condenser. Following industrial experts (Colibri B.V., 2017), AAR chilling at -25 °C
CC

can be driven by hot water at 115 °C, or LP steam of 125 °C. The COP is 0.6 when employing
cooling water at 20 °C as cold sink. If chilling at -10 °C is targeted, then hot water at 90 °C
may be used with a COP of 0.65. Ammonia absorption can replace successfully gas
A

compression refrigeration if the hot source energy is at least three times cheaper than
electricity. The combination of ammonia refrigeration with vapour compression cycle in
cascaded systems is recommended when both thermal and electrical energy are available on
the same site.
 21

In the present situation, an ammonia refrigeration plant that can cover the cooling of
intermediate condensers in gas compression section, 5 MW at -25 °C, as well as chilly water
utility in ABS-1 and C-5, 2 MW at 5 °C, in total 7 MW refrigeration. For estimating the LP
steam consumption COP values of 0.6 and 0.7 were assumed. An amount of 11.9 MW as LPS
matches the requirements of the ammonia-absorption plant.

Heat-pump assisted distillation

T
As described above, the separation of high purity propylene demands very large reflux ratios,

IP
and consequently high energy consumption in reboilers. Employing heat pumping for
propylene purification is illustrated in Dimian et al. (2014). Useful information from

R
industrial viewpoint can be found in Palmer et al. (2012). Typically, ratios reboiler duty to

SC
compressor power over 10 may be obtained. In this case, a heat pump can be implemented for
propylene purification for driving a 6 MW side reboiler (non-visible in Figure 8), located few
trays above the bottom. The heat pump requires about 0.6 MW power and can cover 75%

U
from the overall hot utility, the rest being ensured by LP steam. However, there is an
N
economic advantage only if the cost of vapour compression is advantageous, as available
A
from a heat and power cycle, as it is the case here.
Thermal coupling and utility consumption
M

MTO process offers significant energy saving by thermal coupling of coolers from the
preliminary separation with the reboilers of the olefins separation. Beside duty matching, the
ED

minimum thermal driving should be of minimum 10 °C. Figures 7 and 8 allow the
identification of potential partners. The feasibility of heat exchange in individual cases can be
PT

assessed by using the enthalpy-temperature capability implemented usually in a process

simulator. Table 9 shows the possibilities of thermal coupling of process heat exchangers with
E

reboilers. Thus, the column C-1 can be run by the cooler HX-7, the column C-2 by the cooler
CC

HX-6, while de column C-3 by the water cooler. LP steam is available in abundant amounts.
MTO reactor can supply 14 MW LP steam, while a supplementary amount of 3.6 MW may be
obtained from de cooler HX-4, in total 17.6 MW. This can be used for driving the reboilers C-
A

4 and C-5, in total 5.4 MW. The remaining 12.2 MW may be converted in refrigeration by
means of an ammonia refrigeration plant, as shown before.
 22

Conclusions
Getting ethylene and propylene from methanol by the MTO process represents a major
progress in chemical technology in recent years. MTO is fully sustainable since it allows the
valorisation of renewable resources, as biogas and biomass, as well as of coal resources by a
clean technology. The highly exothermic reaction takes place at 470 °C and 2 bar in a reaction
set-up consisting of fluid bed reactor and regeneration device. The hot reactor effluent has
enough enthalpy for ensuring feed preheating, evaporation and superheating, but the

T
temperature driving force is insufficient for complete heat recovery. This paper proposes an

IP
innovative solution based on Mechanical Vapour Compression. After quenching the reactor
effluent slightly below the dew point, the resulting vapour phase is compressed to lift the

R
temperature with about 50 °C for driving the methanol evaporator, the most energy

SC
consuming unit, as well as the methanol pre-heater. In this way, the reactor effluent ensures
the complete conditioning of the methanol feed in a series of three FEHE units; reactor

U
effluent and methanol feed circulate in the tubular and shell space, respectively. Moreover,
the large amount of water present in the effluent mixture ensures high heat transfer
N
coefficients by water-vapour condensation. This is particularly necessary for driving the
A
evaporator, the largest energy consuming unit. The saved energy may payback the cost of
M

compressor in about one year. In addition, the energy released in reaction is valorised in a
combined heat and power cycle. The power is sufficient for driving the compressors
ED

employed in the process, while the low-pressure steam runs an ammonia-absorption

refrigeration plant that covers the needs of cold utilities for olefins separation.
The separation and purification of olefins is treated as a scheme of minimum five columns.
PT

The pressure in columns is adjusted to maximise the energy saving by process integration.
The key unit ethylene/propylene splitter is designed for high recovery and flexible operation.
E

Since the propylene purification demands a very large reboiler duty, the implementation of a
CC

heat pump is suitable.

Put it in a shell, the proposed conceptual design leads to a compact but efficient flowsheet and
to a process almost neutral from energy viewpoint. As result, both the capital investment and
A

operation costs are at minimum.

 23

Appendix I
The reference case is the separation scheme proposed in a UOP patent (Miller & Semetar,
2002) and evaluated by simulation (Yu & Chien, 2016). Gas effluent is treated by two-step
quench cooling, with intermediate heat recovery for feed pre-heating and superheating, as
displayed in Figure A-1. After reaction, the effluent’s enthalpy is recovered in the units HX-3
for feed super-heating and HX-1 for pre-heating. The methanol evaporation takes place in a
separate heat exchanger HX-2 driven by LP steam. Two quenching towers are used: QT1 for

T
gas cleaning and QT2 for olefin separation. The first is cooled by recycling waste water, while

IP
the second makes use of pump-around. The state of vapour leaving QT1 is close to the dew
point. Heat balance computation shows that a large part of the reactor effluent enthalpy is lost

R
in these quenching operations. The energy loss is 2.0 MW for QT1 and 26 MW for QT2, in

SC
total 28 MW, practically equal with 28.8 MW heat injected in evaporator. This energy can be
saved by adopting the mechanical vapour compression technique, as did in this paper, which
eliminates the need of an expensive utility driven evaporator.
Appendix II U
N
A
Figure A-2 presents the simulation of a combined heat and power cycle. Boil liquid feed
M

water (BFW) at 2.5 bar and 127 °C with a flowrate of 28000 kg/h is pumped up to 40 bar and
converted to steam by taking 15.1 MW of heat from the reactor and 5.8 MW from flue gases,
ED

for isobaric superheating to 600 °C. Then the vapour drives a steam turbine for power
generation by dropping the pressure from 40 to 2.5 bar. Isentropic efficiency of 0.90 and
mechanical efficiency of 0.85 are assumed. The thermodynamic steam model is IAPWS-95
PT

and the turbo-expansion calculation follows the ASME method. The resulting fluid is slightly
superheated vapour at 148 °C. The cycle may supply about 14.9 MW LP steam and 6 MW
E

shaft power.
CC
A
 24

References
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to-olefins process on SAPO-34. Ind. Eng. Chem. Res. 43, 5098–5111
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3. Bildea C.S., Dimian A.C. (1998). Stability and multiplicity approach to the design of
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T
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R
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U
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ED

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T
17. Ludwig, E.E., (2001). Applied process design for chemical and petrochemical plants,

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third edition, vol. 3, Compression equipment, Gulf Professional Publishing.
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U
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editor. Handbook of Petroleum Refining Processes, 3rd ed. McGraw-Hill.
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24. Rostami, R.B., Lemraski, A. S., Ghavipour M., Behbahani R. M., Shahraki B.H.,
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Hamule T. (2016). Kinetic modelling of methanol conversion to light olefins process

over SAPO-34 catalyst. Chemical Engineering Research and Design 106, 347–355.
25. Schmidt, F., Pätzold, C. (2014). Methanol-to-Olefins Processes, in Methanol: the basic
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chemical and energy feedstock of the future, Bertau et al. editors, Springer Verlag,
Berlin, Germany
26. Tian, P., Wei, Y., Ye, M., Liu, Z. (2015). Methanol to Olefins (MTO): From
fundamentals to commercialization. ACS Catalysis, 5, 1922−1938.
27. Ullmann’s Encyclopaedia. Polymers and Plastics (2016), volume 2. Wiley-VCH.
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28. Wei et al. (2014). Fluidized bed reactor and process for producing olefins. Patent US
2014/0121434 A1.
29. Ying, L., Yuan, X. M. Ye, Cheng, Y., X. Li, (2015). A kinetic study of methanol to
olefins process in fluidized bed reactor. Chem. Eng. Res. Des., 100, 179–191.
30. Yu, B., Chien, L (2016). Design and Optimization of the Methanol-to-Olefin Process
Part I: Steady-State Design and Optimization, Chem. Eng. Technol. 39, 12, 2293–
2303; Part II: Comparison of different methods for propylene/propane separation,

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2304-2311.

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31. Ye, M., Li H., Zhao Y., Zhang T., Liu Z (2015). MTO Processes Development: The
Key of Mesoscale Studies, in Advances in Chemical Engineering, vol. 47, Elsevier.

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Natural
gas

FT synthesis Upgrading Fuels

Biogas
Syngas
CO+H2
Biomass Methanol Basic
Olefins chemicals
synthesis
Coal

Polymers

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Figure 1 Valorisation of syngas by hydrocarbon synthesis and methanol to olefin routes

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Figure 2 Vapor pressure versus temperature for key species involved in separations
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Figure 3 Input / Output structure of the MTO process

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Figure 4 Block diagram structure of the MTO process

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Figure 5 Reaction set-up for the MTO process
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Figure 6 Temperature vs. energy flows of feed and effluent streams around the reactor
Left-hand: pinch analysis; Right-hand: effluent stream upgrade by MVC
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Figure 7 Flowsheet of reaction and preliminary separation (a)

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Figure 8 Flowsheet of the olefins separation section (b)

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Figure A-1 Preliminary separation, two step-quench alternative

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Figure A-2 Simulation of the heat and power cycle

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Table 1 Normal boiling points of the components

Component CH4 C2H4 C2H6 C3H6 C3H8 1-C4H8 1-C5H12
NBP, °C -164 -103.7 -89 -47.6 -42 5 36

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Table 2 Material balance for MTO process

Molar Yield
Water
Product Carbon weight (kg / kg MeOH (kg)
(kg)
(kg/kmol) hydrocarbon)
C2H4 2 28 0.40 91.43 51.43
C3H6 3 42 0.40 91.43 51.43
C4H8 4 56 0.11 25.14 14.14
C5H10+ 5 70 0.04 9.14 5.14
Fuel 2 30 0.05 10.67 5.67

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Hydrocarbon 1 227.81 127.81

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5%
Coke, CO, CO2 hydrocarbon 11.39
Total MeOH 239.20

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Ratio MeOH/(C2H4+C3H6) 3.0

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Ratio water/(C2H4+C3H6) 1.6

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Table 3 Input/output material balance for a MTO process

Input Output
Flow rate Yield Flow rate
kg/h %w kg/h
MeOH 100000 0 0
C2H4 40 16722
C3H6 40 16722
C4H8 11 4599

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Total olefins 38043
C5H10+ 4 1672

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Fuel 5 2090
Total hydrocarbon 100 41806

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Water 53432
Coke+gases 4762

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Total kg/h 100000 100000

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Table 4 Flowrate and composition of the outlet reaction mixture

MeOH CH4 C2H4 C2H6 C3H6 C3H8 C4H8 C5H12 Water Total
Flow kg/h 1000 1000 17000 1000 17000 1000 5000 2000 55000 100000

Mass 0.01 0.01 0.17 0.01 0. 17 0.01 0.05 0.02 0.55 1.0
fractions
Table 5 Gas compressors
Unit Mixture Flow [kg/h] Pressure [bar] Stages Power [MW]
CP-1 (a) Water & Hc 108000 1.7→ 2.8 1 3.05

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CP-1 (b) Hydrocarbon 44000 1.5 → 10 2 2.41
CP-2 (b) Hydrocarbon 21217 10 → 20 2 0.38

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CP-3 (b) Hydrocarbon 10735 19.8 → 32 2 0.13
Total 5.97

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Table 6 Heat exchangers

Unit Function Type of heat exchange Duty LMTD U Area
Hot vs. cold fluid MW °C W/m2K m2
HX-1 (a) Pre-heater Vap. cond./Liq. Heating 6.0 37.5 500 320
EDR BEM, hor., hot fl. tubes; Ds 1200/1226 mm; Dt 28/32 Lt 4000 mm; 1 shells 1 parallel 1 series
Tubes 750, At 293 m2 per shell; 1 pass; Total area 293 m2; Total DP shell 0.07, tubes 0.07 bar
HTC shell 1400, tubes 2640, fouling1, U clean 873, dirty 579 W/m2K; MTD 36.0 °C
HX-2 (a) Evaporator Condensation/Evaporation 28.4 36.8 700 1100

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EDR CKU, hor., hot fl. tubes; Ds 1852/1878 Lt 6000 mm; Dt 28/32 mm; 1 shells 1 parallel 1 series

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Tubes 1754, At 1150 m2 per shell, U tubes; Total area 1150 m2; DP shell 0.19 tubes 0.09 bar
HTC shell 4416, tubes 4630, fouling1; U clean 2050, dirty 933 W/m2K; MTD 27.1 °C

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HX-3 (a) Super-heater Gas/Vapour 13.4 92.7 100 1450
EDR BEM, hor., hot fl. tubes; Ds 900/924 mm; Dt 28/32 Lt 5400 mm; 8 shells 4 parallel 2 series

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Tubes 341 At 180.7 m2per shell; 1 pass; Total area 1446 m2; DP shell 0.19 tubes 0.1 bar
HTC shell 308 tubes 179 fouling1; U clean 112, U dirty 105 W/m2K; MTD 88.5 °C;
1) Resistances tubes 0.00035 shell 0.00018 W/m2K
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Table 7 Sizing of separation columns

Unit ABS-1 C-1 C-2 C-3 C-4 C-5
Function Absorber Sep. C1 C2/C3 C2/C3= C3/C3= C4/C5+
NTT 20 23 38 78 148 40
NRT 25 29 48 98 185 50
Feed (Side) 1, 20 1,7,9,10 12 37 100 8 (20)
Ptop [bar] 1.3 30 26 25 12 8
Ttop [°C] 28.1 -69.1 -18.2 -20.5 33.1 13.9

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Tbot [°C] 35.6 19 75.4 3.3 95.4 98.2

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Qc [MW] 0 2.8 4.9 5.9 3.6 2.2
Qr [MW 0 2.8 5.5 5.8 3.6 2.2

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D [kg/h] 44435 1350 17655 16730 17000 1000

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5000 SS
RR / BR - 17.5 2.59 3.3 6.2 / 10
Trays
Passes
Sieve
2
Flex-S
2
Flex-TO
4
Flex-TO
4 U
Flex-TO
4
Sieve
2
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H-tray 0.6 0.6 0.6 0.4 0.4 0.5
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Dc [m] 1.9 1.5 1.9 / 2.3 1.9 / 2.3 3.0/3.3 1.22
DP [bar] 0.15 0.1899 0.3 0.6 1.2 0.3
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Table 8 Refrigeration needs in MTO process

Load [MW] T chiller [°C] Type of refrigeration Energy [MW]
C-2 & C-3 10.7 -30 Two-stage propane 5.35 electricity
C-1 2.5 -75 Cascade propane & ethylene 29.5 electricity
GC section 5.0 -25 Ammonia absorption 8.4 LPS
ABS-1 & C-5 2.0 5 Ammonia absorption 2.9 LPS
Total 19.2

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Table 9 Thermal coupling of heat exchangers and reboilers in the MTO process
Column Duty [MW] Treb. [°C] Heat exch.(a) Duty [MW] T interval [°C]

C-1 2.8 19 HX-7 3.6 85 →30

C-2 5.5 75 HX-5 +LPS 3.5 +2.5 95→85
C-3 5.8 5 HX-6 7 85→30
C-4 3.6 96 LP Steam 4 133→133
C-5 1.8 98 LP Steam 2 133→133

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