11

The production of DME in Spain is mainly carried out by aerosol and fuel industry.
Due to its global increasing

importance regarding energy and environmental advantages, as well as the proper personal interest in the topic,
DME synthesis process was selected in this graduation project.
Nowadays, the indirect synthesis of dimethyl ether is the conventional production method in the industry.
Conditions may be correctly defined and controlled, but it takes two main synthesis steps in the process, whereas
direct synthesis has been recently researched and is about to be implemented as a higher performance method that
occurs in one synthesis step.
Process design and control of DME synthesis
Laura Martín Méndez 15
1. INTRODUCTION
Dimethyl Ether (DME), CH3OCH3, is a gas in ambient conditions, which is non-toxic and non-carcinogenic. It
has a superior solvency power allowing homogeneous blending. It can be obtained from natural gas or from
other raw materials such as coal or biomass. DME has high oxygen and low carbon content; it does not emit
particulate matter (PM) or sulfur oxides (SOx) during combustion due to the absence of sulfur. Due to its clean
combustion properties, it is a promising clean renewable material for the future [1]. Under ambient conditions,
it is a colorless and transparent gas. It is in gas phase at normal pressure and temperature. With applying modest
pressure, it can change to liquid phase. Therefore, it permits easy storage and portability. Its normal boiling
point is -25,1 ºC. Although it causes rubber expanding, it is not corrosive in metals. DME is considered as an
attractive source for next clean energy generation. Main uses of dimethyl ether are power plant fuel, liquefied
petroleum gas (LPG)substitution, diesel oil substitution and hydrogen source for fuel cells. Moreover, DME has
high application in industrial areas. It has been used mainly as aerosol propellant in personal care sector for
many years. It is also widely used for the synthesis of acetic acid and methyl acetate [2]. Since it is a modern
and safe energy source when it is compared to other sources, it has started to take more attention from the
energy market worldwide. Current worldwide production of DME is 150000 tons per year [3]. It is starting to be
used as a clean energy alternative to LPG or gasoline. It can be mixed with LPG for heating and cooking
applications. This mixture can include up to 20 % in volume of DME and there is no need for modifications in
equipment and distribution networks. There are numerous projects under way as demand for environmentally
friendly fuels is increasing interest in blends using DME produced from renewable materials in developed
countries [8]. Compared with diesel fuel, DME has insufficient viscosity and lack of lubricity, but it has good
burning quality and high cetane number. It can be used as fuel in gasoline engines, gas turbines and diesel
engines (30 % DME, 70 % LPG). It can be stored in liquid phase at 0,5 MPa, which is relatively low pressure,
like LPG for gasoline engines. Mack, Nissan, Shanghai Diesel, Volvo and Isuzu have developed heavy vehicles
with diesel engines running with DME [4]. Low cost technologies for DME have been mainly carried out by
JFE Group (Japan), Haldor Topsoe (Denmark) in Europe, Air Products and Chemicals in the United States, and
others. The use of DME as an alternative fuel will be crucial in China, a country with so high pollution rates, in
the near future. Sweden is the leader in the development of bio-DME produced through the gasification and
conversion of black liquor, a byproduct in Sweden's paper and pulp industry [5].
2. AIM
The main objective of this project is to design a process for the production of dimethyl ether.
By comparing first the different processes and methods of synthesis, the best option is determined, in terms of high
yield and simplicity. Process options have been considered regarding feedstock selection and indirect-direct
synthesis methods selection. Availability, prices and required conditions of raw materials need to be analyzed as
well. Production capacity must be determined according to the current demand of dimethyl ether.
Other objectives of the project are to develop the required process control strategies, to research the possible
environmental treatments for the waste streams exiting the process, as well as the economic analysis of the process.
Once the process is determined, the design is planned in order to obtain the required purity of dimethyl ether,
according to the reference articles, which is 99 %. Specifications must be defined in the process simulator Aspen
Plus ® regarding thermodynamic data and process behavior. Simulation of process must be run and results obtained
for further economic analysis. This is done based on the capital investment and manufacturing and operating costs.
Methodology
16 Escuela Técnica Superior de Ingenieros Industriales (UPM)
3. METHODOLOGY
For the creation of this final project report, several steps are followed:
- Literature review and analysis: in order to decide the conditions and methods to obtain the desired product of the
chemical process, a research must be done by review of reference literature and scientific articles. All the required
equipment and components in the process must be assessed and design specifications are figured out from
thermodynamic and stoichiometric data.
- Once the required conditions are clear, design of the process is done with the process simulator Aspen Plus ®.
Several runs and adjustment of each parts of the process are required in order to obtain the desired conditions for
reaction and separation of compounds. Sometimes, an optimization performed with Design Specifications module is
required. Stationary simulation of all process streams and equipment is required every time a process is about to be
developed. It reduces errors in real operation because a scale-up of the process permits equipment design and costs
estimation.
- After simulation and design, including all the utilities, process control strategies may be defined. For this, different
methods are compared and particular cases are studied in each part of the process, based on the Process Control
notes from 4th year, ETSII, UPM. A P&I diagram is finally drawn.
- At the end, environmental regulations are reviewed and several waste treatments are suggested. Safety
considerations are also described regarding security cards of components in the process.
- Economic analysis is done by calculating the total capital cost and the manufacturing and operating costs. Only
feedstocks, equipment and utilities have been taken into account.
Simultaneously, report is written after completion of each part. Future prospective and recommendations have also
been included at the end, after process is analyzed and compared with the other methods previously researched.
For the process simulation, several thermodynamic models can be used in Aspen Plus ®. UNIQUAC is the most
suitable one for the process and has been used. Some important considerations for simulation are explained below,
regarding reactors and distillation columns models in the program.
Reactor models:
There are three different types of reactors that can be used in Aspen: based on kinetics, based on equilibrium and
balance reactors. In each of them, several model can be used depending on the required or known data for
specifications.

Kinetic reactors require specific data of reactions and equilibrium, for a precise simulation. In this group, RCSTR,
RPLUG and RBATCH are included, regarding type of reactor operation and reactants phase.
Equilibrium reactors are used when it is known that the reactions reach equilibrium. REQUIL and RGIBBS can be
chosen in this group.
In balance type reactors, which are of interest for this project, RYIELD can be selected, which is based on mass
balances and stoichiometry is not required. RSTOIC is selected when reaction conversion and stoichiometry are
known. It also permits calculation of heat of reaction. This last model has been selected for all the reactors in this
process simulation.
Distillation models:
DSTWU: it is a rough model used for a previous design of distillation column. By giving required data such as light
and heavy key components recoveries, type of condenser, pressure and minimum reflux ratio, it calculates the real
reflux ratio, number of stages, feed stage, duties and distillate to feed fraction.
DISTIL: it is another rough model for simulation of towers with two products. Number of stages, feed stage, reflux
ratio, distillate to feed ratio, type and pressure of condenser and reboiler are required.
RADFRAC: it is a rigorous model used for simulation of distillation columns, strippers, or reactive distillation
columns. It accepts systems with two or three phases. It requires number of stages, feed stage, type of condenser and
reboiler, pressure and two more specifications, normally reflux ratio and distillate to feed ratio. If results from
simulation do not meet with the requirements, Design of Specifications module can be used in the Radfrac column.
DME markets
4. DME MARKETS
DME is mainly produced for aerosol propellants in small-scale plants. However, it has various potential markets,
such as the following ones:
1) POWER PLANT FUEL
Liquefied natural gas (LNG), liquefied petroleum gases (LPG), fuel oil and coal are used for power plants. Fuel oil
and coal need environmental testing and emission of carbon dioxides is very large compared with DME. LNG and
LPG are relatively clean fuels, but LNG investment cost is very high whereas LPG supply source is limited mainly
by Middle East. However, DME is a clean fuel and the total investment cost would be small since existing LPG
infrastructures could be used with minor modification.
2) LPG SUBSTITUTE
The LPG demand is increasing in Japan, China, India and Southeast Asia. Its price is expected to increase due to
market growth in the future. DME is very competitive against LPG price. Pure DME combustion with household
cooking gas stove for LPG was tested in Japan and it was reported that some modification would be needed. In
China DME is mixed with LPG and the mixture is used as fuel for household cooking gas stove in restaurants
without modification.
3) DIESEL OIL SUBSTITUTE
The present diesel oil is a major source of air pollution from diesel engine of trucks and buses in large cities like
Tokyo. The potential market of diesel oil substitute is larger than LPG. DME is one of the ideal fuels for diesel
engines. DME-based vehicles have been already manufactured in Japan, China and Korea.
1. Road load test data. Engine emissions comparison [7]
4) HYDROGEN FOR FUEL CELLS
Since DME is not toxic at all and has the advantage of decomposition at lower temperature than methane and LPG,
research and development as hydrogen source for fuel cells has been carried out.
Asia has the largest potential DME market as a domestic fuel, being the largest market for this product, where the
capacity has steadily increased and will continue to grow. Plans for construction of new plants in Japan, Iran, and
New Guinea are currently under consideration, as in these places energy demand is rapidly growing.
Japanese government is financially supporting the development of DME technology for gas turbine, diesel engine
cars, fuel cells, as well as establishing laws, regulations and standards for handling DME safely. In Japan, there is a
group named as “Japan DME” composed of Mitsubishi Gas Chemicals, Mitsubishi Heavy Industries, Itochu Corp.
and JGC. They are planning a large scale production of DME using their conventional process in Southeast Asia.
China is already the most advanced country in commercial use of DME as a mixture with liquefied petroleum gas
(LPG). Small DME plants of 500 – 35000 tons per year from coal or natural gas are already in operation for
production of fuel grade DME. China is mainly interested in DME production from their own coal resources as
national policy. A 100000 tons per year DME plant from methanol was built by Luthianhua group in early 2006 [2].
In addition, Shandong Jiutai plans to build several large-scale DME plants from coal.
South Korea is also interested in DME. As KOGAS (Korea Gas Corporation, a public natural gas company
established by the Korean government in 1983) is predominant in handling gas in South Korea, MOU
(Memorandum of Understanding) for market study in South Korea has been signed between TOTAL and KOGAS
quite recently. Their interest of DME is for LPG market as well as fuel for diesel trucks. India is another big
potential market for DME. Their main market would be LPG mixture or alternative to LPG.
Shell, the Anglo-Dutch oil company with interests in the petroleum, natural gas and gasoline refining, offers high
purity Dimethyl ether (DME) for all cosmetic and technical uses. Shell has decades of experience in the
manufacturing of DME. The abundant capacity of the DME production unit makes the Wesseling plant one of the
World‘s biggest DME manufacturers. Shell DME 99,99 % is used as aerosol propellant in the cosmetics and paint
industry, as blowing agent for foams and insulation boards, component for refrigeration fluids, the production of
dimethyl sulfate and many other technical areas [8].
The only plant in the world where dimethyl ether is produced from biomass is in the city of Pitea (Sweden). In this
plant, transport biofuels are produced from gasification of biomass from the paper industry. Therefore, Volvo
Trucks, the truck division of the famous automotive company, is already conducting tests to use a new biofuel called
Bio-DME, which comes from biomass. This fuel emits far less carbon and the engine less noise. The initiative,
which has European funding, is the result of the union of several companies in the technology, energy and transport
fields, among which Chemrec (manages the plant in Piteå), Total and Volvo. Thanks to the Program Market
Oriented Prototyping at the University of Salamanca (Spain) a research team of this institution has
DME markets
developed a web application to coordinate use of raw materials in plants with biofuel in cars. They do not rule out its
application to the Swedish production.
Methanex, a Canadian company, which is the global leader in methanol industry supply, distribution and marketing,
recognized in the early 2000s that DME could create significant new markets for methanol as a fuel. Other big
companies dedicated to DME production are JFE Steel Corporation (Japan), Total and Lurgi, a German chemical
and construction company. Total is interested in large-scale production of DME as a new clean fuel. From 2001,
International DME Association (IDA) serves as the global voice for DME industry. The following figure shows the
evolution of markets and uses of dimethyl ether:
2. Evolution and development of DME markets and applications [4]
5. PROCESS OPTIONS AND SELECTION

There are three different raw materials from which dimethyl ether can be obtained: natural gas, coal and biomass.
From these, several processes such as steam reforming, auto thermal reforming or even tri-reforming may be used in
order to obtain synthesis gas. Once this gas is obtained, there are two routes for dimethyl ether synthesis: direct and
indirect methods. In the first one, DME is obtained directly from synthesis gas. In the indirect synthesis, which is the
conventional process used in the industry, syngas is converted to methanol and then methanol dehydration occurs to
produce dimethyl ether.
All the feedstock options are being compared in order to select the best option for this process. Likewise, synthesis
methods are analyzed and best or most feasible one is selected, between direct and indirect.
5.1. Feedstock selection
Biomass as a feedstock:
Some agricultural residues such as corn stalks, wood chip and rice husk are well-known biomasses, which can be
used as feedstock in DME production. The main disadvantage of the biomass usage could be pointed out as its
variations in shape and size. This leads to some difficulties in drying and pulverizing steps.
Moreover, biomass crude gas contains approximately 10 ppm of sulfur that might cause catalyst deformations. On
the other hand, biomass technology is not developed enough to adjust to dimethyl ether production yet. Hence, it
will not be selected as raw material in this process.
Coal as a feedstock:
Synthesis gas production from coal is called gasification. After this, it would be converted to dimethyl ether by
catalytic reactions. In order to achieve the desired ratio of hydrogen to carbon monoxide, the water-gas shift reaction
takes place. Then sulfur and carbon dioxide removal, which is crucial for environmental regulations, occurs by
absorption with a proper solvent. After this removal, the clean gas is preheated and fed to the reactor. Finally, the
purification step occurs by using distillation. Moreover, as a carbon rich feedstock, coal provides electricity in
addition to DME. Recycling unconverted gas to the reactor enables more conversion. When it is recycled, more
electricity power is obtained.
Carbon dioxide emissions, water scarcity and unsteady prices of coal can be pointed out as disadvantages. Coal is a
carbon-rich feedstock and when it burns it releases large amount of carbon dioxide. If carbon dioxide is not captured
or recycled, it can strongly damage the
Process options and selection
atmosphere, increasing greenhouse effect and global warming. Coal industry is a threat for the arid regions that
contain coal resources since coal-based industries are water-intensive and require large amounts of water for
production. Producing one ton of methanol from coal requires approximately 20 m3 of fresh water and also coal
mining consumes substantial water resource [9]. If DME industry expands in those regions, water scarcity would be
an inevitable consequence. The instability of coal prices is also an obstruction for coal selection.
As mentioned above, the main benefit of this raw material is the carbon-rich property of coal that provides more
energy so that electricity could be sold or used in the plant.
Natural gas as a feedstock:
The most common feedstock used worldwide for DME production is natural gas. It gives a suitable solution for
environmental conservation and secure energy supply, in addition to profitability. It also has lower production costs
compared to other raw materials. The composition of the natural gases are changing according to the location where
they are taken from. Generally, natural gas contains more than 85 % of methane.
Many feedstocks can be used to produce synthesis gas via steam reforming. Originally synthesis gas for the
production of methanol comes from coal. Nevertheless, syngas not produced from natural gas can contain a wide
range of impurities. Moreover, conversion of biomass to syngas is typically low-yield. Since natural gas is a
particularly flexible feedstock, suitable for use in plants of all sizes, synthesis gas is most commonly produced from
it. Hence, natural gas has selected as a feedstock for DME synthesis process.
5.2. Direct and indirect synthesis methods
Dimethyl ether production process from synthesis gas comprises three main steps: water-gas shift reaction, methanol
synthesis reaction and methanol dehydration.
Traditionally, DME has been produced by indirect synthesis. It is a two-catalytic-step process. Firstly, synthesis gas
is converted to methanol in the following reactions:
2CO + 4H2 ↔ 2CH3OH ΔH298= -43,4 kcal/mol (1)
CO2+ 3H2 ↔ CH3OH+H2O ΔH298= -11,9 kcal/mol (2)
Subsequently, DME is produced by dehydration of methanol in the following reaction:
2CH3OH ↔ CH3OCH3 + H2O ΔH298= -5,6kcal/mol (3)
Synthesis gas may be obtained by steam reforming in the presence of Ni/α-alumina catalyst. Nowadays, the main
companies owning the necessary technology for DME production by indirect synthesis are Haldor Topsoe, Lurgi,
Mitsubishi Gas Chemical Company, China
Southwestern Research Insitute of Chemical Industry, Toyo Engineering Corporation and China Energy (Jiutai
Group)
Worldwide methanol production is mainly controlled by two companies: Johnson Matthey (ICI process) and Lurgi.
It occurs in presence of heterogeneous Cu/Al/ZnO catalyst. Final step, dimethyl ether production, is carried out in
presence of acid solids. Zeolites, γ-alumina and silica-alumina catalysts are the most commonly used.
Direct synthesis, a relatively new route of synthesis, occurs only in one step and one reactor is used. Inside it,
several reactions take place to convert synthesis gas to dimethyl ether. Several companies, including Haldor Topsoe,
Japan JFE Holdings Company and Korea Gas Corporation, have developed direct DME synthesis technologies [3].
The following reactions take place:
2CO + 4H2 → 2CH3OH ΔH298= -43,4 kcal/mol (4)
2CH3OH → CH3OCH3 + H2O ΔH298= -5,6 kcal/mol (5)
CO + H2O → CO2 + H2 ΔH298= -9,8 kcal/mol (6) [3]
Methanol synthesis reaction, methanol dehydration and water-gas shift reaction (the last one above) occur in the
same reaction vessel, after synthesis gas is previously obtained. The overall equation can be expressed as:
3CO + 3H2 → CH3OCH3 + CO2 ΔH298= -58,8 kcal/mol (7)
One of the most remarkable direct synthesis is JFE process, carried out in the company plant of Ohno, Japan.
Reactions take place in a slurry bed reactor. The synthesis catalyst developed by the JFE Group is active and
selective for the three step reactions under conditions of 260 ºC and 5 MPa. As can be seen in equation (4), molar
ratio of CO and H2 is 1:1 in this process.
The previous reaction of steam reforming to obtain the syngas is shown below. By conventional reforming or even
authotermal reforming, a higher H2/CO is obtained. Hence, the required molar ratio of 1 can be achieved by
recycling the byproduct CO2.
2CH4 + O2 + CO2→ 3CO + 3H2 + H2O (8)
Due to the two catalytic steps that take place, bifunctional catalysts are required in the direct synthesis of dimethyl
ether. One function of methanol synthesis, based on Cu, and a methanol dehydration function, based on an acid
solid. This way, methanol synthesis reactions and water-gas shift reaction occur on Cu-based catalyst whereas
methanol dehydration to DME takes place on the acid catalyst. Recently, new materials have been researched such
as heteropolyacids (HPAs) catalysts, which present excellent acid properties, very important for dimethyl ether
synthesis.
Process options and selection
The complexity of indirect process could be considered as a disadvantage. It requires more equipment and streams,
which involves higher cost for the process. Nevertheless, the indirect method permits more flexibility in the process
as it occurs in different steps and reactors. Any anomaly in feedstock supply or in upstream processes could be
easily compensated.
In addition, catalysts can be different in both reactors, imply acceptable costs and do not influence other reactions. If
all the reactions occur in the same vessel with a bifunctional catalyst, any activity problem or disturbance may ruin
the process. Apart from this, higher temperatures are required for the effectiveness of direct synthesis and catalyst
activity. This limits the reaction from a thermodynamic point of view, since global reaction is highly exothermic.
Moreover, the large decrease of volume leads to high operation pressures, normally higher than 4 MPa. Therefore,
control of reaction becomes an arduous task.
Indirect synthesis method is easier to operate and control. Moreover, since it is the most widely used nowadays,
there is more information in the reference literature for implementation of operation and process conditions. For all
of these reasons, indirect synthesis has been selected for this project.
All in all, dimethyl ether will be obtained from natural gas, since it is more beneficial from both environmental and
economic points of view, and indirect synthesis is used. Steam reforming of crude methane is preferred for
implementation of the process with Aspen Plus®.
3. Block diagram of indirect synthesis of DME from natural gas
6. INDIRECT SYNTHESIS OF DME

Indirect synthesis of dimethyl ether occurs in two consecutive steps: methanol synthesis from
syngas and methanol dehydration to obtain DME. For methanol synthesis, a previous reaction of
methane or natural gas reforming is occurred. In total, three reactors are present in the process.
Basic structure of the whole process is described by the following block diagram.
4. Block diagram of DME indirect synthesis
6.1. Components physical properties
The following table shows the physical properties of all pure components, from Aspen Plus ®
Database:
Table 1. Physical properties [10]
Methanol CH3OH 32.04 337.67 80.32 512.68 175.53 20.98
Oxygen O2 31.998 90.19 50.43 154.65 54.36 - Dimethyl ether C2H6O 46.07 248.36 53.1 400.05 131.62 - Methane
CH4 16.043 111.65 46.00 190.56 90.69 - Hydrogen H2 2.02 20.397 12.93 33.18 13.96 - Carbon dioxide CO2 44.01
185.35 73.81 304.15 216.59 21.15
Carbon monoxide CO 28.01 81.62 37.04 134.18 68.05 - Water H2O 18.02 373.15 220.77 647.11 273.16 46.53
CRITICAL PRESSURE (bar) CRITICAL TEMPERATURE (K) MELTING POINT (K)
DENSITY OF LIQUID AT 25ºC (Kmol/m3 )
PHYSICAL PROPERTIES
COMPONENT NAME FORMULA MOLECULAR WEIGHT (Kg/Kmol)
NORMAL BOILING POINT (K)
Indirect synthesis of DME
6.2. Reaction stoichiometry and kinetics
The first step of the reaction is synthesis gas production. It is produced by steam reforming of methane. The reaction
equations and kinetics are given below.
CH4 + H2O ↔ CO + 3H2 (9)
r =1,527 exp (-14,820/RT) ��4 1.014

��2�� −0.9577 (10)
Assuming order 1.014 as 1 and order -0.9577 as -1, the rate equations become:
r =1,527 exp (-14,830/RT) PCH4 PH2O (11)
Where;
Ea =14,82 kcal/g mol
k=1,527 g mol/gcat h [11]
Although steam reforming is carried out at high temperature, a catalyst (Ni/α-Alumina) is still required to accelerate
the reaction due to the very high stability of methane [12].
After carbon monoxide is obtained from methane, it is partially converted to carbon dioxide, by the water-gas shift
reaction [13].
CO+ H2O ↔ CO2+ H2 (12)
r = k ��2��
1+��.��2��
/��2�� where; Keq=exp (4577,8/ T – 4,33) (13)
Next, synthesis gas experiments two reactions where methanol is produced.
CO + 2H2 ↔ CH3OH (14)
CO2+ 3H2 ↔ CH3OH+H2O (15)

The original catalyst for methanol synthesis was ZnO-Cr2O3, only active at high temperatures. New catalysts based
on copper oxides mixed with alumina have been developed. They are more active at lower temperatures and
pressures and resist sintering. Heterogeneous catalyst Cu/Al/ZnO is used in this process. ZnO promotes Cu activity
in these systems. Only Cu-based catalysts are not active for methanol production. Although methanol synthesis is a
very old process, there is not unanimity about the active centers nature and behavior of ZnO yet. The typical atomic
composition for these catalysts is 6/3/1. Aluminum is in charge of increasing dispersion of copper and inhibit its
sintering. Reaction mechanism is also unclear and controversial thesis have been presented by different authors in
the literature. A bifunctional
mechanism is general accepted and there are several models depending on the synthesis gas composition.
Reaction kinetics is shown below [14]:
r = �� 1.9��2 0.9

(1+��2 1.7
��2+��
1.5��) (16)
Where;
k = 2,034* 108 exp (-14061/RT) (17)
KCO = 66,63exp (1588,2/RT) (18)
KCO2 = 139507exp (-17551/RT) (19)
Finally, dimethyl ether synthesis takes place in the presence of ɣ-alumina catalyst by the following reaction.
2CH3OH ↔ CH3OCH3 + H2O (20)
For catalysts with Lewis-type acidity, such as ɣ-Al2O3, dehydration mechanism suggested by Jain and col is the
most widely accepted. Oxygen anions with excess of electrons present basic behavior, whereas aluminum is
deficient of electrons (acid behavior). Methanol molecules are adsorbed on basic and acid adjacent centers.
Immediately, both adsorbed species react by means of a Langmuir-Hinshelwood mechanism, forming a DME
molecule on the basic center. One proton reacts with the adsorbed OH on the acid center, forming a H2O molecule.
The following figure illustrates this mechanism:
5. Methanol dehydration to DME mechanism [15]
Kinetics equations are expressed below [16].
R = k0 exp (-Ea/RT) Pmethanol (21)
Where;
Ea=80,48kJ/mol; k=1,21*106 ��

�� ℎ �� 3
6.3. Thermodynamics data In the following figures, liquid-vapor equilibrium diagrams at 1 bar for methanol and
dimethyl ether are illustrated [10]. 6. Liquid-vapor composition diagram for DME 7. T-xy equilibrium diagram for
methanol
8. Liquid-vapor composition diagram for methanol
6.4. Process design
6.4.1. Basis of design
According to the demand of DME in Spain and part of Europe, the desired capacity of DME production plant has
been determined in 90000 tons per year.
Since operational efficiency of a continuous process is higher compared to batch processes, a continuous process has
been designed for DME production. It is also the best option for a large process which occurs in three steps (three
reactions). There is a recycle stream of mainly carbon dioxide in order to achieve the desired hydrogen-carbon
monoxide ratio. This also helps meeting environmental regulations for gas limit emission values.
The most relevant parts of the process are reaction and separation sections. The process design is based on these
sections and its operation conditions, explained below.
In the first step, methane reacts with steam and converts natural gas to carbon monoxide and hydrogen in the
presence of Ni/α-Alumina catalyst. A second reaction which converts CO in CO2 occurs in lower extent. The first
one is a highly endothermic reaction whereas the second (called water-gas shift reaction) is exothermic. Standard
reaction enthalpies are shown as follows.
CH4 + H2O = CO + 3H2 ΔHº298 = 206 kJ/mol [12]
CO + H2O = CO2 + H2 ΔHº298 = -41 kJ/mol [12]
As a result, syngas is produced as a mixture of CO, CO2 and H2 at temperatures above 800 ºC. In the steam
reformer, several burner units are used to provide the required heat for the highly endothermic reaction. Combustion
of fuel occurs inside them and heat is recovered from the hot flue gases by convection.
Coke formation, by decomposition of methane or disproportionation of CO, may occur in the reformer. It may lead
to the deactivation of the catalyst or cause total blockage of the reformer tubes, developing hot spots. To avoid this,
steam is added in excess. Using a larger than stoichiometric quantity of steam also enhances conversion due to the
lower partial pressure of methane. Typical H2O/C ratios for industrial processes are shown in table 2.
Table 2. Typical H2O/CO ratios [12]

Steam reforming is hindered by elevated pressure because the number of molecules increases in the reaction.
Nevertheless, hydrogen production is always carried out at relatively high pressure to avoid the necessity of
compression for transportation at downstream units. At 30 bar, equilibrium conversion is only complete at over 1400
K, which is not feasible due to metallurgical constraints. The effect of pressure and ratio on methane conversion as a
function of temperature is represented below:
9. Effect of pressure and H2O/C ratio [12]
Typical reformer conditions for industrial syngas based processes are shown in table 3.
Table 3. Typical reformer conditions for industrial processes [12]
From this table and looking at figure 9, conversion of methane can be calculated as 85 % for a ratio of 3 in the feed,
in order to obtain syngas suitable for the subsequent methanol production. Therefore, operation conditions for steam
reformer has been has been selected as 1173 K and 17 bar and CH4 conversion can be found as 85 %. With this,
conversion of carbon monoxide in the water-gas shift reaction can be estimated as 36 %.
As already mentioned, RSTOIC reactor model is chosen for all the reactors, based on stoichiometry and conversion
data. It represents an ordinary gas phase reactor, such as a PFR, but conditions of a steam reformer are defined.
Design specifications for this reactor in Aspen Plus ® are displayed, with corresponding reactions and conversions:
Table 4. Reactions and conversions in the steam reformer
Table 5. Steam reformer specifications
In the next reactor, methanol is obtained as follows:
CO + 2H2 = CH3OH ΔHº298 = -90,8 kJ/mol [12]
CO2 + 3H2 = CH3OH + H2O ΔHº298 = -49,6 kJ/mol [12]
Classic synthesis methods for methanol synthesis operate at high pressures because original catalyst (ZnO-Cr2O3)
was only active at high temperature. Nowadays, more active catalysts can be used at lower temperatures, which is
also more favorable from a thermodynamic point of view. A new generation of Low-Pressure plants have arisen by
maintaining the same conversion as in the classical process.
Apart from activity, selectivity is crucial for catalyst development since methanol is less stable than other products
like methane. Temperature is also critical because high activity catalysts are sensitive to sintering. It must not exceed
570 K, at which unacceptable sintering may occur [12]. A small amount of CO2 increases the catalyst activity.
The ideal synthesis gas for methanol production has a H2/CO ratio of about 2. Lower ratio leads to by-products
formation; a higher value results in a less efficient plant due to the excess of hydrogen, although it could be
recovered for reuse. By using naphtha as raw material, this ratio is obtained, but with natural gas it is higher than 2.
Nevertheless, natural gas has a lower cost than naphtha and higher availability. In this process, with natural gas as
feedstock, the ratio can be adjusted by recycling of carbon dioxide. This would tend to reverse the water-gas shift
reaction.
In the following figure, influence of temperature and pressure on CO conversion to methanol can be analyzed.
10. Equilibrium CO conversion to methanol (feed H2/CO = 2 mol/mol) [12]
Modern processes for methanol synthesis use low pressures in order to decrease cost and save compressive energy.
The differences among them rely on reactor design and the way heat of reaction is removed. There are three main
modern processes:
 The ICI process: adiabatic reactor with a single catalyst bed. Intermediate cooling by quenching with cold reactant
gas at different heights.
 The Haldor Topsoe process: several adiabatic fixed-bed reactors arranged in series with intermediate coolers to
remove heat of reaction.
 The Lurgi process: cooled multi-tubular reactor, nearly isothermal, with catalyst particles located in the tubes and
cooling by boiler feed water (BFW).
For this process, selected operation conditions for methanol reactor, according to figure 10 and catalyst activity
range, are 220 ºC and 100 bar. A conversion of 95 % is assumed for carbon monoxide. For CO2, 19 % has been
estimated. A reactor similar to the Lurgi process one has been selected. Synthesis gas enters an isothermal reactor
with cooling (BFW) in presence of Cu/Al/ZnO catalyst, which passes through the tubes. Reactions and
thermodynamic specifications in Aspen Plus ® are shown hereafter.
Table 6. Methanol synthesis reactions and conversions
Table 7. Methanol reactor specifications
The third step is dimethyl ether synthesis, where the desired product is obtained. It occurs by methanol dehydration,
which is an exothermic reaction, in presence of ɣ-alumina.
2CH3OH = CH3OCH3 + H2O ΔHº298 = -11,9 kJ/mol [17]
The best temperature control can be achieved with a fluidized bed reactor. However, due to the high installation
costs and the low stability of the bed, a fixed bed reactor is usually preferred. Methanol conversion may occur in
temperatures between 250 ºC and 368 ºC. In order to avoid side reactions, minimum required pressure is 10,4 bar.
Temperature must never exceed 400 ºC, as severe deactivation of catalyst can occur.
For this process, an isothermal fixed bed reactor has been used for DME synthesis. Compared to adiabatic operation,
not so high temperatures are reached at the reactor exit stream, which saves energy in the downstream units before
separation occurs. Cooling is applied by BFW in order to remove heat of reaction from the bed. Operation
conditions are 330 ºC and 15 bar, with a feasible conversion of 80 % [17].
In this case, another gas phase RSTOIC reactor was used for simulation. The specified reaction and thermodynamic
specifications from Aspen Plus ® are shown below.
Table 8. DME reaction and conversion
Table 9. Thermodynamic specifications of DME reactor.
After describing the design and operation conditions for all the reactors, separation units shall be briefly explained.
In the first part of the process, methanol synthesis, target purity is fixed as 99 %. After methanol reactor, gas-liquid
separation is required to separate and recycle unreacted incondensable gases. This takes place in a flash drum and
optimal thermodynamic conditions should be figured out. Due to the volatile nature of all the incondensable gases in
the process, such as methane or CO, only methanol equilibrium graphs and boiling point are taken into account for
determination of temperature. Selected value is 1ºC, the minimum possible value, so that most of it exits the flash in
liquid phase by the bottom. For the pressure, a sensitivity analysis is done with Aspen Plus ®. It expresses the
influence of pressure in molar composition of the top stream exiting the flash unit. Only the compounds showing
significant variations are represented in figure 11. Carbon monoxide and methane have practically the same mole
fraction in top stream when pressure is varied.
11. Sensitivity analysis in the flash drum
As the graph shows, there is a limit value of pressure around 10 bar from which the carbon dioxide content of top
stream decreases, which means that higher amount of it goes with methanol bottom stream, increasing impurities in
the product. Nevertheless, although relative high pressures are favorable for separation of methanol, this is not
feasible and acceptable for this process, as negative temperatures would be required. Different values lower than 10
bar are tried, 5 bar is found as the first value requiring negative temperatures, and finally 4 bar is selected. Operation
conditions in the flash drum are specified as 1 ºC and 4 bar.
For separation of methanol in the first distillation column, atmospheric pressure is determined, in basis of
thermodynamic equilibrium diagrams and no pressure drop is considered for simplicity. In order to obtain the
required purity of methanol, the reflux ratio might be varied in the tower. The following sensitivity analysis shows
its influence in distillate composition.
12. Sensitivity analysis of Reflux ratio-composition for CH3OH Due to the low normal boiling point of dimethyl
ether (-24,64 ºC), it is not distilled at atmospheric pressure. The design pressure for DME distillation column has
been selected as 5 bar, and there is no pressure drop in the tower. For optimization of separation, again a sensitivity
analysis of distillate composition when varying the reflux ratio should be done. It is represented below:
13. Sensitivity analysis of Reflux ratio-composition for CH3OCH3 6.4.2. Feedstock conditions The chosen raw
material used in this project for the production of dimethyl ether is natural gas, a fossil fuel which main component
is methane but also contains small amounts of different saturated hydrocarbons. In Spain, natural gas is imported
from Algeria and Libya in a price of 600 € per 1000 m3 [18]. Its molar composition is: 86.15 % CH4 12.68 % C2H6
Sensitivity Results Curve

VARY 1 B4 COL-SPEC MOLE-RR
XH2O XCH3OCH3
1,00 1,25 1,50 1,75 2,00 2,25 2,50 2,75 3,00 3,25 3,50 3,75 4,00 4,25 4,50 4,75 5,00 5,25 5,50 5,75 6,00 6,25 6,50
6,75 7,00 7,25 7,50 7,75 8,00 8,25 8,50 8,75 9,00 0 5,0e-6 1,0e-5 1,5e-5 2,0e-5 2,5e-5 3,0e-5 3,5e-5 4,0e-5 4,5e-5
0,935 0,940 0,945 0,950 0,955 0,960 0,965 0,970 0,975 0,980 0,985 0,990 XCH3OCH3 XH2O
0.68 % of N2
0.4 % of C3H8
0.09 % of C4H10 [19]
Natural gas has a high ignition temperature, even above 1100 ºC and it is roughly 40% lighter than the air. It can be
extracted from the sedimentary porous rocks. It is stored and transported as liquefied gas by large pipelines as well
as LNG transportation ships. For very large distances, a complex network of pipelines is the safest mean of
transportation. There are three major systems for transportation process: gathering, interstate and distribution. Low
pressure and small diameter pipelines are required in gathering systems in order to transport the gas from natural
sources to the processing plant. Interstate pipelines carry natural gas across state boundaries. The gas is brought
from production areas to “gate stations” where distribution companies deliver it to homes and businesses.
The other raw material required in the process is steam.
Battery limits:
For designing of the process, crude methane is used as representative compound of natural gas. Since it is the main
component in the gas, specified above, and it is the compound of interest which reacts in the steam reformer to
obtain synthesis gas, this feed stream is taken as 100 % methane for simulation with Aspen Plus ®. The other
feedstock, steam, is considered directly at the required thermodynamic conditions and no upstream treatment is
taken into account.
Regarding the production capacity (90000 tons/year of DME) and the required H2O/C ratio, adequate flow rates for
feed streams have been estimated. Conversion values in all the reactors have been taken into account for these
calculations. As a result, 1590,6 kmol/h of steam enter the process at 205 ºC and 17 bar. Crude methane at 60 ºC and
17 bar flows with a rate of 530 kmol/h.
14. Gas natural supplier countries. Jan-Dec. 2014 period. [20]
6.5. Results of simulation

6.5.1. Process flow diagram
15. Methanol synthesis process flow diagram (PFD 1)
16. DME synthesis process flow diagram (PFD 2)
Process flow diagram of the indirect dimethyl ether synthesis process is shown in figures 15 and 16. The whole
process is represented in two steps, each of them in a different PFD. First PFD shows methanol production step,
where synthesis gas is obtained from methane. Second PFD shows dimethyl ether synthesis from methanol
dehydration, the second step of this process, and starts with the feeding methanol stream that comes from the first
step of the whole process.
Crude methane has been selected as the representative compound of natural gas, being the only feed to the process,
apart from steam. Steam is fed in excess, in a H2O/methane ratio of 3:1, which is the most suitable for the synthesis
gas used for methanol production, as already explained. Hence, 1590,6 kmol/h of steam water enters the process in
stream 1 at 205 ºC and 17 bar. Crude methane enters the process as stream 2, with a flowrate of 530,2 kmol/h, at
60ºC and the same pressure. Heat integration in E-101 and E-102 is used to heat methane to 850oC before steam
reforming. The hot reactor exit stream (number 7 in the PFD 1) is used for this. Methane leaves the second heat
exchanger as stream 4 and is mixed with streams 1 and 5, the recycle stream of the process. The resultant stream,
numbered as 6, enters the first reactor with 7227,7 kmol/h at 438,4 ºC and 17 bar.
Synthesis gas is obtained by reforming of methane in a steam reformer, which has been simulated as an endothermic
fixed bed reactor, R-101. In the steam reforming, a highly endothermic reaction converts methane to CO and H2,
and subsequently, part of the CO is again reacted with steam water to produce carbon dioxide, in a sufficiently
exothermic reaction called shift conversion or water-gas shift reaction. The suitable conditions for steam reforming
reaction to obtain syngas used for methanol synthesis are 850ºC and 17 bar. The required heat to reach this high
temperature that permits the endothermic reaction is provided by combustion reactions in the furnace units of the
steam reformer. The obtained syngas exits the reactor at 900oC and 17 bar as stream 7.
As already mentioned, heat integration between entering methane and reaction outlet stream occurs in equipment E-
101 and E-102. Therefore, temperature of the syngas decreases to 821,3oC, after both heat exchangers (stream 9),
and the pressure remains at 17 bar. In order to reach the feasible operation conditions for methanol production in the
next reactor, compression section for the syngas must be set. Moreover, cooling of syngas needs to be performed for
the reaction to take place; first, heat exchanger named as E-103 cools syngas stream up to 200 ºC by using boiler
feed water as utility. Two compressors are used to reach the required pressure of 100 bar in stream 14. In order to
avoid increase of temperature above 220ºC, intermediate heat exchangers are used after each step of pressure
increase in this compression section.
At the end, syngas becomes ready for the methanol production as stream 14, which flows in a rate of 8263,3 kmol/h
at 200 oC and 100 bar to R-102. Methanol production occurs when CO and CO2 react with H2 respectively in two
reactions, both highly exothermic. An isothermal reactor with cooling, similar to Lurgi reactor, is used. Stream 15
leaves the reactor with 7380,8 kmol/h and approximately 6 % methanol (mole fraction). The following heat
exchangers, E106 and E-107, are used to decrease temperature and pressure before separation section. Here phase
change occurs while cooling.
Stream 17 enters the flash drum S-101 at 45ºC and 10 bar for a liquid-gas separation in order to split the unreacted
volatile gases from the methanol-water mixture. Top stream (18) containing those gases will be partly recycled to
the process. Bottom stream (19) enters a distillation column (T-101) at 1ºC and 4 bar, for further separation of
methanol from the liquid mixture. As a very low amount of volatile gases is still present in this stream, a partial
condenser has been used in the distillation of methanol, to release these gases at the top vapor stream. Light key
component flows in the top liquid stream at 436,2 kmol/h and is the product obtained in the first part of the process,
methanol of 99,2 % molar purity at 39,3ºC and 1 bar. The heavy key component is water which flows at 1001,8
kmol/h through the bottom stream of the column with a temperature of 98,8ºC and a pressure of 1 bar.
The two streams of light unreacted gases coming from the flash drum and distillation column are mixed and the
resultant stream, numbered as 23, is later split in other two: a purge stream and the recycle of this first part of the
process. In order to take advantage of the recycle and reuse the reactants to improve the yield in the reactors and
process, the minimum feasible fraction of stream 23 has been purged in stream 24, released at 1 bar. The rest amount
of gases flows at 4990,9 kmol/h; 1,12ºC and 1 bar in stream 25, containing mainly H2 and CO2. It is compressed to
reach 17 bar; resultant stream, 5, is mixed with feed streams of water and methane to enter the steam reformer.
Produced methanol in PFD 1 continues to the second part of the process (PFD 2) for DME production. Stream 21 is
mixed with the recycle of gases from this second part of the process, stream 26, and the resultant stream (27) needs
to be heated before entering the reactor R-201. Methanol dehydration occurs in gas phase at temperatures around
250-330 ºC and pressure of 15 bar. Initial liquid stream will finally reach 230ºC and 15 bar after the second heat
exchanger, E-202, in the stream 28 (gas phase).
Reaction to obtain DME, the final desired product, occurs in a fixed bed reactor with cooling in presence of ɣ-
alumina catalyst. Reactor outlet flow, stream 30, has 537,7 kmol/h of gas mixture with a 40,4 % of dimethyl ether, at
330ºC and 15 bar. Again pressure and temperature need to be decreased for separation of the product, by using a
heat exchanger (E-203) where part of the vapor stream changes to liquid phase.
Stream 31 enters a distillation column, T-201, at 100ºC and 5 bar where DME is obtained. A partial condenser is
used in order to release the volatile incondensable gases through the top vapor stream. In the top liquid stream, light
key component, the aimed DME, flows at 14,4ºC and 5 bar, in a flowrate of 213,5 kmol/h with a molar purity of
98,6 %. Heavy key component of this distillation is water, but it is not very pure. It contains methanol that must be
separated in another distillation column (T-202). In this one, a partial condenser is used but only vapor stream leaves
the top in order to recycle. Bottom stream contains 214,3 kmol/h of water that exits the process at 97,3ºC and 1 bar.
Both top vapor streams from the distillation columns are mixed first and resultant stream (37) consists of 109,99
kmol/h of incondensable gases at 62,5ºC and 1 bar that must be partly recycled. A purge stream (38) releases a
minimum fraction of this stream out of the process. Recycle stream (26) contains a total amount of 101,5 kmol/h of
gas at 63,5ºC and 1 bar which returns to the start of this part of the process, to be mixed with the methanol feed
stream.
17. Aspen Plus® Main Flowsheet for methanol production
18. Aspen Plus Main Flowsheet for DME production

6.5.2. Streams results
After simulation of both parts of the process for DME indirect synthesis with Aspen Plus ® Software v8.8, results
have been displayed and saved. Input and output streams are explained in table 10 for the whole process of DME
synthesis.
Table 10. Input and output streams results
With these results, global mass and energy balances of the whole process of DME synthesis have been calculated in
table 11.
Table 11. Global mass and energy balances
Negative value of total enthalpy indicates that high amounts of energy are produced in the process by means of heat,
which could be recovered for reuse.
Simulation results of the main process streams are shown hereafter, with flow rates, compositions and
thermodynamic conditions.
Steam CH4 DME (product) Stream No. 1 2 33 22 24 36 38 Molar flow rate (kmol/h) 1590,57 530,20 213,48
1001,85 835,98 214,27 8,49
Mass flow rate (kg/h) 28654,56 8505,87 9827,84 18115,54 5038,01 3899,56 279,56
Composition (mole fracc.) H2O: 1 CH4 : 1 CH3OCH3 :0,986 CO2 : 0,014 H2O: 0,995 CH3OH: 0,005
H2 : 0,892 CO2 : 0,085 CH4 : 0,015 H2O: 0,001 CO: 0,003 CH3OH: 0,004
H2O: 0,987 CH3OH: 0,013
CH3OH: 0,934 CH3OCH3 : 0,061 CO2 : 0,004 H2O: 0,001
T (ºC) 205 60 14,40 98,84 1,12 97,27 62,54 P (bar) 17 17 5 1 1 1 1 Vapor fraction 1 1 0 0 1 0 1 Liquid fraction 0 0 1
1 0 1 0 Heat (kW) -103952,42 -10770,19 -12245,73 -77748 -8537,23 -16613,83 -468,49
INPUT OUTPUT Waste streams
Stream No. 1 2 33 22 24 36 38 OUTPUT-INPUT Molar flow rate (kmol/h) 1590,57 530,20 213,48 1001,85 835,98
214,27 8,49 153,29
Mass flow rate (kg/h) 28654,56 8505,87 9827,84 18115,54 5038,01 3899,56 279,56 0,07
Heat (kW) -103952,42 -10770,19 -12245,73 -77748 -8537,23 -16613,83 -468,49 -890,67
Stream 1 2 3 4 5 6 7 8 9 INPUT Eq. M-101 E-101 E-102 M-101 M-101 R-101 E-102 E-101 E-103 OUTPUT Eq. E-
101 E-102 C-103 M-101 R-101 E-102 E-101 Phase VAPOR VAPOR VAPOR VAPOR VAPOR VAPOR VAPOR
VAPOR VAPOR
Mole Flow (kmol/h) CH4 0 530,20 530,20 530,20 75,45 605,65 87,82 87,82 87,82 H2O 1590,57 0 0 0 5,93 1596,50
884,89 884,89 884,89 CO 0 0 0 0 14,55 14,55 338,59 338,59 338,59 H2 0 0 0 0 4553,33 4553,35 6300,63 6300,63
6300,63 CO2 0 0 0 0 435,33 435,33 629,12 629,12 629,12 CH3OH 0 0 0 0 22,27 22,27 22,27 22,27 22,27 Mole
Fracc. CH4 0 1 1 1 0,015 0,084 0,011 0,011 0,011 H2O 1 0 0 0 0,001 0,221 0,107 0,107 0,107 CO 0 0 0 0 0,003
0,002 0,041 0,041 0,041 H2 0 0 0 0 0,892 0,630 0,762 0,762 0,762 CO2 0 0 0 0 0,085 0,060 0,076 0,076 0,076
CH3OH 0 0 0 0 0,004 0,003 0,003 0,003 0,003 Mass Flow (kg/h) CH4 0 8505,87 8505,87 8505,87 1210,41 9716,28
1408,86 1408,86 1408,86 H2O 28654,56 0 0 0 106,87 28761,43 15941,49 15941,49 15941,49 CO 0 0 0 0 407,48
407,48 9484,09 9484,09 9484,09 H2 0 0 0 0 9178,97 9179,01 12701,31 12701,31 12701,31 CO2 0 0 0 0 19158,97
19158,99 27687,44 27687,44 27687,44 CH3OH 0 0 0 0 713,67 713,67 713,67 713,67 713,67 Mass Fracc. CH4 0 1
1 1 0,039 0,143 0,021 0,021 0,021 H2O 1 0 0 0 0,003 0,423 0,235 0,235 0,235 CO 0 0 0 0 0,013 0,006 0,140 0,140
0,140 H2 0 0 0 0 0,298 0,135 0,187 0,187 0,187 CO2 0 0 0 0 0,623 0,282 0,408 0,408 0,408 CH3OH 0 0 0 0 0,023
0,011 0,011 0,011 0,011 Total Flow (kmol/h) 1590,57 530,20 530,20 530,20 5106,87 7227,66 8263,32 8263,32
8263,32 Total Flow (kg/h) 28654,56 8505,87 8505,87 8505,87 30776,37 67936,86 67936,86 67936,86 67936,86
Temperature (ºC) 205 60 721 800 441,34 438,39 900 889,24 821,34 P (bar) 17 17 17 17 17 17 17 17 17 Vapor
Fracc. 1 1 1 1 1 1 1 1 1 Liquid Fracc. 0 0 0 0 0 0 0 0 0 Enthalpy (kJ/mol) 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 Enthalpy
(kJ/s) -0,2 -0,2 -0,2 -0,2 -0,2 -0,3 -0,3 -0,3 -0,2
Stream 10 11 12 13 14 15 16 17 18 INPUT Eq. C-101 E-104 C-102 E-105 R-102 E-106 E-107 S-101 M-102
OUTPUT Eq. E-103 C-101 E-104 C-102 E-105 R-102 E-106 E-107 S-101 Phase VAPOR VAPOR VAPOR
VAPOR VAPOR VAPOR MIXED MIXED VAPOR
Mole Flow (kmol/h) CH4 87,82 87,82 87,82 87,82 87,82 87,82 87,82 87,82 87,54 H2O 884,89 884,89 884,89
884,89 884,89 1004,42 1004,42 1004,42 6,90 CO 338,59 338,59 338,59 338,59 338,59 16,93 16,93 16,93 16,91 H2
6300,50 6300,50 6300,50 6300,50 6300,50 5298,58 5298,58 5298,58 5298,19 CO2 629,12 629,12 629,12 629,12
629,12 509,59 509,59 509,59 498,47 CH3OH 22,27 22,27 22,27 22,27 22,27 463,47 463,47 463,47 21,34 Mole
Fracc. CH4 0,011 0,011 0,011 0,011 0,011 0,012 0,012 0,012 0,015 H2O 0,107 0,107 0,107 0,107 0,107 0,136
0,136 0,136 0,001 CO 0,041 0,041 0,041 0,041 0,041 0,002 0,002 0,002 0,003 H2 0,762 0,762 0,762 0,762 0,762
0,718 0,718 0,718 0,894 CO2 0,076 0,076 0,076 0,076 0,076 0,069 0,069 0,069 0,084 CH3OH 0,003 0,003 0,003
0,003 0,003 0,063 0,063 0,063 0,004 Mass Flow (kg/h) CH4 1408,86 1408,86 1408,86 1408,86 1408,86 1408,86
1408,86 1408,86 1404,41 H2O 15941,49 15941,49 15941,49 15941,49 15941,49 18094,90 18094,90 18094,90
124,33 CO 9484,09 9484,09 9484,09 9484,09 9484,09 474,20 474,20 474,20 473,64 H2 12701,06 12701,06
12701,06 12701,06 12701,06 10681,31 10681,31 10681,31 10680,52 CO2 27687,38 27687,38 27687,38 27687,38
27687,38 22426,78 22426,78 22426,78 21937,50 CH3OH 713,65 713,65 713,65 713,65 713,65 14850,49 14850,49
14850,49 683,91 Mass Fracc. CH4 0,021 0,021 0,021 0,021 0,021 0,021 0,021 0,021 0,040 H2O 0,235 0,235 0,235
0,235 0,235 0,266 0,266 0,266 0,004 CO 0,140 0,140 0,140 0,140 0,140 0,007 0,007 0,007 0,013 H2 0,187 0,187
0,187 0,187 0,187 0,157 0,157 0,157 0,303 CO2 0,408 0,408 0,408 0,408 0,408 0,330 0,330 0,330 0,621 CH3OH
0,011 0,011 0,011 0,011 0,011 0,219 0,219 0,219 0,019 Total Flow (kmol/h) 8263,19 8263,19 8263,19 8263,19
8263,19 7380,80 7380,80 7380,80 5929,36 Total Flow (kg/h) 67936,54 67936,54 67936,54 67936,54 67936,54
67936,54 67936,54 67936,54 35304,32 Temperature (ºC) 200 414,81 200 303,32 200 220 110 45 1 P (bar) 17 50 50
100 100 100 30 10 4 Vapor Fracc. 1 1 1 1 1 1 0,874 0,819 1 Liquid Fracc. 0 0 0 0 0 0 0,126 0,181 0 Enthalpy
(kJ/mol) -56,2 -49,4 -56,2 -52,1 -56,2 -67,4 -75,8 -80,6 -36,2 Enthalpy (kJ/s) -129103,5 -113474,5 -129103,5 -
119577,3 -129103,5 -138274,4 -155458,4 -165273,0 -59544,1
Stream 19 20 21 22 26 27 28 29 INPUT Eq. T-101 M-102 M-201 M-201 E-201 E-202 R-201 OUTPUT Eq. S-101
T-101 T-101 T-101 D-201 M-201 E-201 E-202 Phase LIQUID VAPOR LIQUID LIQUID MIXED LIQUID
LIQUID VAPOR
Mole Flow (kmol/h) CH3OH 442,12 4,57 432,77 4,78 94,75 527,52 527,52 527,52 H2O 997,52 0,002 0,45 997,07
0,096 0,545 0,545 0,545 CH3OCH3 - - - - 6,21 6,21 6,21 6,21 CO 0,02 0,02 0 0 0,001 0,002 0,002 0,002 H2 0,51
0,51 0,002 0 0,016 0,017 0,017 0,017 CO2 11,12 8,13 2,99 0 0,42 3,41 3,41 3,41 CH4 0,28 0,26 0,02 0 0,017 0,036
0,036 0,036 Mole Fracc. CH3OH 0,305 0,339 0,992 0,005 0,933 0,981 0,981 0,981 H2O 0,687 0 0,001 0,995 0,001
0,001 0,001 0,001 CH3OCH3 - - - - 0,061 0,012 0,012 0,012 CO 0 0,001 0 0 0 0 0 0 H2 0 0,038 0 0 0 0 0 0 CO2
0,008 0,602 0,007 0 0,004 0,006 0,006 0,006 CH4 0 0,019 0 0 0 0 0 0 Mass Flow (kg/h) CH3OH 14166,60 146,58
13866,95 153,07 3035,93 16902,89 16902,89 16902,89 H2O 17970,57 0,028 8,07 17962,47 1,74 9,81 9,81 9,81
CH3OCH3 - - - - 286,02 286,02 286,02 286,02 CO 0,57 0,55 0,018 0 0,035 0,052 0,052 0,052 H2 1,03 1,027 0,003
0 0,032 0,035 0,035 0,035 CO2 489,32 357,74 131,58 0 18,40 149,98 149,98 149,98 CH4 4,45 4,14 0,32 0 0,27 0,58
0,58 0,58 Mass Fracc. CH3OH 0,434 0,287 0,990 0,008 0,908 0,974 0,974 0,974 H2O 0,551 0 0,001 0,992 0,001
0,001 0,001 0,001 CH3OCH3 - - - - 0,086 0,016 0,016 0,016 CO 0 0,001 0 0 0 0 0 0 H2 0 0,002 0 0 0 0 0 0 CO2
0,015 0,701 0,009 0 0,006 0,009 0,009 0,009 CH4 0 0,008 0 0 0 0 0 0 Total Flow (kmol/h) 1451,57 13,49 436,23
1001,85 101,50 537,74 537,74 537,74 Total Flow (kg/h) 32632,55 510,06 14006,95 18115,54 3342,42 17349,37
17349,37 17349,37 Temperature (ºC) 1 39,27 39,27 98,84 62,54 99,15 120 230 P (bar) 4 1 1 1 1 15 15 15 Vapor
Fracc. 0 1 0 0 0,998 0 1 1 Liquid Fracc. 1 0 1 1 0,002 1 0 0 Enthalpy (kJ/mol) -275,1 -305,8 -237,8 -279,4 -1986,7 -
2304 -227,5 -191 Enthalpy (kJ/s) -110937,2 -1145,9 -28813,6 -77748 -56016,2 -344151,9 -33987,2 -28531
Table 12. Streams results
Stream 30 31 32 33 34 35 36 INPUT Eq. E-203 T-201 M-202 T-202 M-202 OUTPUT Eq. R-201 E-203 T-201 T-
201 T-201 T-202 T-202 Phase VAPOR MIXED VAPOR LIQUID LIQUID VAPOR LIQUID
Mole Flow (kmol/h) CH3OH 105,50 105,50 0 0,015 105,49 102,67 2,82 H2O 211,55 211,55 0 0 211,55 0,10 211,45
CH3OCH3 217,22 217,22 2,77 210,49 3,95 3,95 0 CO 0,002 0,002 0,001 0,001 0 0 0 H2 0,017 0,017 0,017 0 0 0 0
CO2 3,41 3,41 0,45 2,95 0 0 0 CH4 0,036 0,036 0,018 0,018 0 0 0 Mole Fracc. CH3OH 0,196 0,196 0 0 0,329 0,962
0,013 H2O 0,393 0,393 0 0 0,659 0,001 0,987 CH3OCH3 0,404 0,404 0,850 0,986 0,012 0,037 0 CO 0 0 0 0 0 0 0
H2 0 0 0,005 0 0 0 0 CO2 0,006 0,006 0,139 0,014 0 0 0 CH4 0 0 0,01 0 0 0 0 Mass Flow (kg/h) CH3OH 3380,58
3380,58 0 0,47 3380,11 3289,85 90,26 H2O 3811,18 3811,18 0 0 3811,18 1,88 3809,30 CH3OCH3 10006,96
10006,96 127,82 9697,02 182,13 182,13 0 CO 0,052 0,052 0,038 0,015 0 0 0 H2 0,035 0,035 0,034 0,001 0 0 0 CO2
149,98 149,98 19,94 130,04 0 0 0 CH4 0,58 0,58 0,29 0,29 0 0 0 Mass Fracc. CH3OH 0,195 0,195 0 0 0,458 0,947
0,023 H2O 0,220 0,220 0 0 0,517 0,001 0,977 CH3OCH3 0,577 0,577 0,863 0,987 0,025 0,052 0 CO 0 0 0 0 0 0 0
H2 0 0 0 0 0 0 0 CO2 0,009 0,009 0,135 0,013 0 0 0 CH4 0 0 0,002 0 0 0 0 Total Flow (kmol/h) 537,74 537,74 3,26
213,48 321 106,73 214,27 Total Flow (kg/h) 17349,37 17349,37 148,11 9827,84 7373,42 3473,86 3899,56
Temperature (ºC) 330 100 14,40 14,40 120,56 63,29 97,27 P (bar) 15 5 5 5 5 1 1 Vapor Fracc. 1 0,580 1 0 0 1 0
Liquid Fracc. 0 0,420 0 1 1 0 1 Enthalpy (kJ/mol) -1928,7 -2226,8 -2118,8 -2065 -2604,1 -1982,7 -2791,4 Enthalpy
(kJ/s) -288094 -332619,3 -1920,9 -122457,3 -232194,8 -58779,2 -166138,3
6.5.3. Equipment results After specifying suitable operation conditions for equipment in order to obtain a high yield
in the process and the required purity of DME, simulation was done and results obtained. Mass and energy balances
for each equipment have been saved and analyzed. REACTORS Design specifications and operation conditions for
reaction sections have been already explained in “Basis of design” part. Simulation results from reactors are shown:
 Steam reformer (R-101)
Table 13. Steam reformer results summary In this reactor, a highly endothermic reaction occurs, reforming of
methane. Thus, simulation gives a high positive value for heat duty (65305,6 kW): the required heat for the reaction
to occur, which is provided by a fuel oil in the furnaces of the steam reformer. Actually there is an enthalpy
decrease, as can be seen below.
Table 14. Steam reformer mass and energy balances
Table 15. Phase equilibrium in steam reformer
 Methanol reactor (R-102)
Table 16. Methanol reactor results summary In this case, exothermic reactions takes place for methanol synthesis.
Thus, simulation gives a high negative value for heat duty (-9184,91 kW). It is the released heat after reaction. Now
enthalpy of input stream increases after reaction and process stream is heated. In order to avoid accumulation of this
heat in the reactor, which would inhibit conversion, cooling water is used as refrigerant, absorbing this heat.
Table 17. Methanol reactor mass and energy balances
Table 18. Phase equilibrium in methanol reactor  DME reactor (R-201)
Table 19. DME reactor results summary Methanol dehydration is another exothermic reaction where heat is
released, but this time with a much lower value (-279,172 kW). Again enthalpy of input stream increases after
reaction and utility usage is required to avoid increasing temperatures inside unit R-201.
Table 20. Mass and energy balances for DME synthesis reactor
Table 21. Phase equilibrium in DME synthesis reactor
In order to avoid runaway of exothermic reactions, due to the high temperatures that can arise, cooling water is used
as refrigerant. The following table shows flow, duty and cost values of the utilities in R-102 and R-201.
Table 22. Utility results for exothermic reactors
DISTILLATION COLUMNS
In “METHODOLOGY”, distillation models in Aspen Plus ® have been described. As mentioned, first of all,
DSTWU model must be used for simulation. Final design will be done with RADFRAC. Optimization with Design
Specifications may be performed if necessary.
T-101
For the first synthesis process, methanol purity target is 99 % mole, according to the references. By applying the
suitable operation conditions and defined split fraction, distillated methanol has been obtained with 99.2 % molar
purity, with the use of RADFRAC design, T101. There is no need for optimization with Design Specifications
module. A previous and first design approach was done by using DSTWU, which requires recoveries specification.
Thus, a SEP2 block has been used in advance to obtain the feasible recoveries and the distillate vapor fraction. This
block was defined by split fraction values of light or heavy key and the rest of light components.
For this column, atmospheric pressure is selected and there is no pressure drop between condenser and reboiler. A
good design parameter for the reflux ratio considers it as 1,3 times the minimum reflux ratio (Rmin). This can be
specified in DSTWU with minus sign (-1,3). With all these data, DSTWU is simulated and here are the results:
Utility type BFW BFW Utility duty (kW) -9184,91 -279,17 Utility usage (kg/h) 85206,95 419,83 Utility cost (€/h)
1,90 0,01
Equipment CH3OH reactor DME reactor
Table 23. Simulation of DSTWU for T-101
Now RADFRAC block can be specified, by using first approach information from DSTWU results. Design is
completed and can be displayed. Column T-101 is designed with 21 stages. Feed stage is number 16 (with feed
above stage). Target mole purity can be achieved with a reflux ratio of 1,293 and a distillate to feed fraction of
0,309. Partial condenser with vapor and liquid distillate is used for separation of light gases on the top of the tower.
Table 24. Specifications of RADFRAC distillation for T-101
Table 25. Radfrac results summary for T-101 Table 26. Split fraction results for Radfrac T-101
T-201
For the second part of the process, where the desired product is obtained, two distillation columns are used. From
the first one, DME is separated, whereas in the second one, only a gas stream exits the top of the tower with the
remaining methanol for recycle. Therefore, the interest of a high performance separation relies on the first tower, T-
201.
The same procedure has been used for design and simulation: SEP2, previous DSTWU approach and RADFRAC;
but in this case, optimization was required to meet purity requirement for dimethyl ether. Design Specifications
module was run several times by adjusting reflux ratio until achievement of target. For T-201, operation pressure
(constant along the whole tower) is 5 bar. Partial condenser with vapor-liquid distillate is selected.
Table 27. Specifications of first RADFRAC distillation for T-201
Temperature 39,27 ºC Heat duty -10630,2 kW Distillate rate 449,72 kmol/h Reflux rate 581,93 kmol/h
Temperature 98,84 ºC Heat duty 13858,34 kW Bottoms rate 1001,85 kmol/h Boilup rate 1224,06 kmol/h Boilup
ratio 1,222 Bottoms to feed ratio 0,690
Condenser/top stage performance
Reboiler/bottom stage performance
Relative volatilities of dimethyl ether and the remaining methanol respect to the water can be seen in the following
figure, for each stage of the column. DME is quite more volatile than methanol and its separation is not an arduous
task.
19. Rel-vol. H2O of DME and methanol along the column
After first simulation of RADFRAC for T-201, molar purity of desired DME is 86,9 %. The requirement for this
process is 98,6%. Therefore, molar reflux ratio may be varied to improve the purity.
By defining the target purity in Design Specifications and giving a variation range for the reflux ratio in Vary,
optimization of separation is achieved and complete results of Radfrac simulation are shown:
Table 28. Radfrac results summary for T-201. Split fraction results.
Dimethyl ether is finally obtained with a molar purity of 98,6 % as it has been specified in the design of this process.
It has been possible with a molar reflux ratio of 1,489 as obtained in Design Specifications iteration.
Block B4: Relative Volatility
Stage
RelVol-H2O
1 2 3 4 5 6 7 8 9 10 11 12 0 25 50 75 100 125 150 175 200 225 250 275 CH3OH CH3OCH3
Temperature 120,56 ºC Heat duty 498,68 kW Bottoms rate 321 kmol/h Boilup rate 48,90 kmol/h Boilup ratio 0,152
Bottoms to feed ratio 0,597

Table 29. Design Specifications module results for T-201
Distillation column T-201 is designed with 12 stages. Feed stage is number 8 (with feed above stage). Vapor and
liquid compositions of DME along the column are represented:
20. Vapor and liquid phase DME fractions along the column
Streams results of this tower, with DME exit stream number 33, are in table 30:
Table 30. Streams results for final simulation of T-201
T-202
In the last distillation tower, T-202, methanol is separated from water and recycled to the feed of dimethyl ether
reactor. The column operates at 1 bar and there is not pressure drop along it.
Block B4: Composition Profiles
Stage
Mole fraction
1 2 3 4 5 6 7 8 9 10 11 12 0,0
0,2
0,4
0,6
0,8
1,0 Liquid mole fraction CH3OCH3 Vapor mole fraction CH3OCH3
Stream 31 32 33 34 Mole Fracc. CH3OH 0,196 0 0 0,329 H2O 0,393 0 0 0,659 CH3OCH3 0,404 0,850 0,986 0,012
CO 0 0 0 0 H2 0 0,005 0 0 CO2 0,006 0,139 0,014 0 CH4 0 0,005 0 0 Total Flow kmol/hr 537,74 3,26 213,48 321 T
(ºC) 100 14,40 14,40 120,56 P (bar) 5 5 5 5
Partial condenser with only vapor distillate is selected. Simulation and design of tower is performed as before, but
there is not any purity target: no optimization is needed. However, split fraction is always at the maximum possible
value when design, in order to obtain a good separation and increase the process yield with the recycle of methanol.
Specifications and results for block T-202 are shown below:
Table 31. RADFRAC Specifications for T-202

Table 32. Radfrac results summary for T-202. Split fraction results.
FLASH DRUM, S-101
In “Basis of design”, sensitivity analysis for T and P operating in the flash drum have been explained. Selected
conditions for liquid-gas separation are 1 ºC and 4 bar. Table 33 shows thermodynamic results of flash separation.
Table 33. Flash S-101 results summary. Phase equilibrium in flash drum S-101
Temperature 97,27 ºC Heat duty 2044,03 kW Bottoms rate 214,27 kmol/h Boilup rate 178,14 kmol/h Boilup ratio
0,831 Bottoms to feed ratio 0,668
As it is displayed, 5213,14 kW are produced in this flash unit.
HEAT EXCHANGERS
As mentioned before, several heat exchangers are used in the process in order to heat or cool reactors feed and exit
streams.
At the beginning of the process, two shell and tube heat exchangers heat methane feed stream to reach the suitable
temperature for steam reforming to take place. Heat integration occurs between two process streams, inside each of
them. Steam reforming exiting stream, with a temperature of 900ºC is the heating medium, and methane feed is the
cold stream. Since geometrical specifications are unknown, shortcut countercurrent model has been selected. Exit
temperatures have been specified so that both heat exchangers have the same area.
Specifications and design results for each of these heat exchangers, from Aspen Plus displays, are shown below:
Table 34. Heat exchanger E-101 specifications
Table 35. Heat exchanger E-101 results summary
Table 36. Heat exchanger E-101 thermal results

Table 37. Heat exchanger E-102 specifications
Table 38. Heat exchanger E-102 results summary
Table 39. Heat exchanger E-102 thermal results
The rest of heat exchangers use cooling water or steam as utility, no process streams interchange heat. All of them
are specified with the adequate pressure and temperature in order to maintain suitable conditions for reaction or
separation sections.
Compression loop of methanol synthesis process consists of two compressors set in series with intermediate cooling.
This means that alternate heat exchangers are required when increasing pressure in order to avoid excessive
temperatures before quench methanol reactor. Simulation displays of heaters E-104 and E-105 (after first
compressor and before methanol reactor) are shown in the tables:
Table 40. Heat exchanger E-104 simulation
After the first reactor, gas stream is at 210 ºC and needs to be cooled before entering separation section.
Temperature and pressure must be decreased to separate incondensable gases in the flash drum. Therefore, two
heaters are used and the last one is displayed:
Another heating section is required before last reactor, DME synthesis fixed bed reactor. Methanol distillate from
the first part of the process is liquid phase and not enough warm for the reaction. Heat exchangers E-201 and E-202
reach temperature of methanol stream up to 230 ºC and keep pressure constant at 15 bar. Although feeding methanol
enters this part of the process at 1 bar, mixing with recycle stream (26) rises pressure up to 15 bar. Apart from the
higher yield achieved by recycling unreacted gas, energy is saved this way. Here are the simulation results of E-202:
Afterwards, another heat exchanger (E-203) is required before separation of dimethyl ether. This time, both pressure
and temperature are lowered before entering distillation tower. Results are in table 44.
COMPRESSORS
Equipment C-101 and C-102 has been already explained when describing compression loop before methanol
synthesis reactor. Pressure change in all of these equipment has usually a maximum ratio of 3:1. For this reason, two
compressors are needed in the mentioned loop. Another compressor is used in stream 25, to rise pressure of recycle
gases before mixing with the feeds, up to 17 bar. Specification and results of C-102 and C-103 are displayed:
Table 45. Compressor C-102 specifications
Table 46. Compressor C-102 results summary
Table 47. Compressor C-103 specifications
Table 48. Compressor C-103 results summary
Process control
7. PROCESS CONTROL
Regulation and control equipment are applied to obtain stable conditions and provide efficient and economic
production. In general, the adjustments are done by regulating the flow rates with the use of control valves placed on
pipes. As it is illustrated in the piping and instrumentation diagram, sometimes only indicators are used for the
pressure. Level control must be used when operating with liquids in a process unit and pressure control in case of
vapor phase, in order to assure the stability of the process and avoid accumulations. Temperature control is generally
required and plays a crucial role for the operation of the process units within the specified limits. Composition
control is also very important for achieving the specifications of products in distillation columns.
7.1. Heat Exchangers
Temperature of the outlet streams of heat exchangers must be controlled in order to assure their correct performance
and achieve the desired operating conditions in downstream or upstream process units.
First heat exchangers, E-101 and E-102, utilize a process stream, syngas from reactor outlet, for heating natural gas
(or crude methane) feed stream. Heat integration occurs with no need for control, as all the variables are already
determined (temperatures in this case); otherwise process operation conditions would be altered. Methane flow rate
is already manipulated and controlled with the recycle stream. This one contributes to keeping the suitable ratio of
H2/CO at the syngas, and reactor exit stream cannot be manipulated either; this would affect conversion and
reaction performance. Since E-103, E-104, E-105, E-106, E-107 and E-203 are used to cool down process streams, if
the temperature of their outlet streams increases, it is above the set point, the valve must be opened to increase the
cooling utility flow rate. The heat exchangers set at the beginning of the second part of the process (DME synthesis),
E-201 and E-202, are used to increase the temperature of process streams, in order to get the required condition for
DME synthesis reaction. Hence if the temperature of the exit stream increases above the set point, the control valve
is closed to decrease the flow rate of the heating utility, and vice versa.
7.2. Compressors
The pressure control in these equipment must be applied by manipulating the spin speed of the engine. Pressure of
the exit stream could be at most 3 times of the pressure of the inlet stream. If the ratio between exit and inlet stream
is larger than 3, intercoolers are used.
7.3. Reactors
Reactors used in this process are all tubular for vapor phase, where the most important variable in terms of control is
temperature. Since equilibrium reactions take place in all of them, by controlling temperature the pressure will be
consequently determined, for a defined
conversion. Thus, there is no need for pressure control; however, a pressure indicator has been set in each reactor for
convenience.
In the first one, the steam reformer, temperature control is carried out by manipulation of the fuel oil flow rate in the
furnaces of the reformer. As a highly endothermic reaction occurs, combustion reaction in those furnaces release
heat providing the required high temperature. The other two reactors are exothermic, so cooling utility has been used
in order to avoid the so-called run-away of the reaction, or the reverse reaction. The worse situation in this type of
reactors would be a very high temperature. It would cause the inhibition of the exothermic reaction. This may
happen if there is not an efficient control system and the heat produced by the exothermic reaction is not correctly
eliminated. The solution for this problem is to control the maximum temperature reached at the tubular reactor. As
temperature is not uniform along the bed, several measurements of temperature at different sections must be done
and transmitted. This system consists of several maximum temperature selectors, so that the maximum value is
transmitted as a signal to the controller, which compares it with the set point. If this temperature is higher than the
set point, valve of cooling utility must be opened.
7.4. Flash drum
In this unit accumulation risk must be reduced to the minimum. This means that liquid level cannot overlap the flash
and pressure must be controlled as well to avoid explosions. Pressure is measured inside the flash drum and the
signal is transmitted (PT) to the controller (PIC), which compares it with the set point value and sends an action to
the control valve at the vapor top outlet stream. Likewise, level of liquid is controlled with the bottom stream flow
rate.
7.5. Distillation columns
The purpose of control in distillation towers is to obtain the products with the desired purity and to assure stability
and safety of the operation. Generally, distillation requires a refined design of operation conditions and geometrical
parameters; an adequate control system is important to assure distillation is completed successfully and desired
specification is achieved. Pressure and liquid level must be controlled in the tower, with manipulation of
respectively vapor and liquid streams leaving the column. Quality control of distilled product is performed by
controlling the temperature in one tray of the column. Manipulating the liquid reflux stream flow rate, this
composition is controlled. Bottom liquid composition must remain constant by regulating the heat duty, provided by
steam.
In the following table, process control analysis is summarized, and variables concerning each process unit are listed.
The following P&I diagram shows all the required equipment and instruments for the process control of DME
indirect synthesis.
Process control
21. P&ID of methanol synthesis
22. P&ID of DME synthesis
Waste treatment and environmental considerations
8. WASTE TREATMENT AND ENVIRONMENTAL

CONSIDERATIONS
The undesirable materials which are formed during the operation, wastes, have negative effects on the environment
and society. Thus, proper waste treatment strategies must be applied to reduce the negative impacts. Environmental
regulations are getting stricter, so the appropriate choice of waste treatment is crucial. According to the Industrial
Emissions Directive 2010/75/EU, main pollutants to consider for limit emission values are the following [22]: 1.
Sulfur oxides 2. Nitrogen oxides 3. Carbon monoxide 4. Volatile organic compounds (VOC) 5. Metals and their
compounds 6. Powder 7. Asbestos 8. Chlorine and its compounds 9. Fluorine and its compounds 10. Arsenic and its
compounds 11. Cyanides 12. Substances with carcinogenic or mutagenic properties. 13. Polychlorinated
dibenzodioxins and polychlorinated-dibenzofurans The process contains by-products such as carbon monoxide
(CO), carbon dioxide (CO2), hydrogen and water. From the environmental point of view, the most important part of
dimethyl ether manufacturing process is carbon dioxide recycling stream. The negative environmental impact of
carbon dioxide release lies in a greenhouse effect gas emissions, which contributes to global warming. Hence, most
of it must be removed by using a recycling stream. Ideally, all the amount must be recycled in the process, but
simulation of a continuous stationary process like this does not permit its complete recycle. In order to avoid
accumulation of material, a purge stream is required in this process.
Apart from CO2, although it is present in much lower concentration, carbon monoxide must be treated, as it is
highly toxic and hazardous for the atmosphere and living organisms. Although CO is a weak greenhouse effect gas,
it has its own effects on climate. Its presence affects concentrations of other greenhouse effect gases, including
methane, tropospheric ozone and carbon dioxide [23]. Moreover, there are official regulations for CO permitted
emission values, as it is one of the major atmospheric pollutants.
A high amount of hydrogen is not consumed in the first part of the process and must be recycled and purged. Thus,
the most abundant compound in the first purge stream is H2, which must be recovered for further usage. A slight
amount of carbon dioxide, together with CO and the unreacted gases, is purged and must be treated before
atmospheric release. Hydrogen must be also separated and recovered with an appropriate technique.
Waste water streams from the bottoms of distillation columns should be sent to a waste water treatment unit before
disposal for purification and removing of methanol, which is highly dangerous for the environment and aquatic
species. Biological treatment would eliminate organic materials to meet environmental requirements of LEV.
Composition of waste streams and proper waste treatment strategy for this process are explained in the following
points. Both methanol and DME synthesis have purge gases and require a previous waste treatment before release to
the atmosphere. In methanol synthesis, most abundant compound in purge stream is H2, which needs to be
recovered, whereas in DME synthesis a low amount of hydrogen is purged and membrane separation for its recover
is not worth. Therefore, in both processes carbon monoxide and dioxide must be removed, but in the first synthesis,
hydrogen and unreacted methane are also treated.
8.1. CO2 removal
Carbon dioxide is the second most abundant compound in the purge gases stream of methanol synthesis process. It is
present in a molar composition of 8,52 %. For environmental reasons, it must be removed by absorption before
releasing to the atmosphere.
CO2 can be removed by several methods: chemical or physical absorption processes, with aqueous solutions,
glycols (Rectisol process) or cold methanol (Selexol process); adsorption with alumina or zeolites; frosting; or
separation with membranes [24]. Nevertheless, it is usually removed by absorption. Several solvents can be used for
this, but amine solutions are the most common ones nowadays. MEA (monoethanolamine) and DEA
(diethanolamine) are some examples; although they exhibit high mass transfer rates, their regeneration is energy
intensive [12]. Table 49 shows a comparison of several solvents for absorption of carbon monoxide in terms of
energy requirements.
Table 49. Energy requirements for CO2 removal systems [12]
In order to avoid corrosive compounds from decomposition of MEA, inhibitors are used in the solution. They permit
higher amine concentrations, which lead to lower heat of regeneration, as a result of the decrease in the circulation
rates. Another common process for CO2 removal is absorption with a hot potassium carbonate solution, carried out
in a decarbonization unit at high pressure. Various additives, mentioned above in the table, can be used to increase
mass transfer rates and inhibit corrosion.
This process requires lower regeneration energy due to the weak bonding between the carbonate and CO2. The
following reaction occurs for regeneration of the solvent. Providing the necessary heat and decreasing pressure,
bicarbonate is obtained:
CO2 + H2O + K2CO3 → 2 KHCO3
MDEA (methyldiethanolamine) is, as can be shown in the previous table, the solvent with the lowest energy
requirement for regeneration, and for this reason it is considered as one of the best options for carbon dioxide
removal. The so low heat of regeneration is due to the weakness of the CO2-amine bonding, in comparison to the
other solvents. Besides, it does not form corrosive compounds, and additives just serve to improve mass transfer.
All in all, since absorption with methyl diethanolamine method is preferred for CO2 removal before atmospheric
release of purged gases, it has been selected in methanol synthesis process.
In the second part of the process, a low amount of CO2 is purged (1,54 kg/h), and prices of solvents for absorption
process must be analyzed and compared in order to decide which the best option is, from both technical and
economical points of view.
8.2. CO removal
Carbon monoxide is a highly toxic gas; it is considered as a major factor contaminating the Earth atmosphere. In
addition, it has harmful effects for the human health and reduces oxygen delivery to the body organs and tissues
when entering bloodstream.
Direct release to the atmosphere is forbidden, according to the official environmental regulations (Directive
2010/75/EU on industrial emissions. Integrated pollution prevention and control). In this instruction, several gas
compounds concentrations are restricted. This means that limited emission values are stated for each of them, and
values for CO are shown below:
LEV (mg/Nm3) Average value/day 50 8-hour average value 100 Average value/10 min 150
Table 50. Limit emission values (mg/Nm3) of CO for industrial releases [22]
According to these values, 0,039 kg/h is the limit emission flowrate for CO.
It is clear that a high amount of carbon monoxide must be removed with a suitable and efficient technique. Possible
methods are flaring, adsorption with molecular sieves, polymeric membranes, absorption with aqueous electrolyte
solutions, or other solvents.
Flaring is a high-temperature oxidation process used to burn combustible components, mostly hydrocarbons, of
waste gases from industrial operations. Atmospheric oxygen would enter through the vent system of the plant to
react with CO by the following combustion reaction:
CO (g) + 1/2 O2 (g) → CO2 (g)
Since this reaction leads to an increase in the CO2 concentration, and this compound cannot be released in high
amount either, flaring is not chosen as a method for CO removal. Despite the simplicity of the operation and the
high yield of carbon monoxide elimination, NOx and other compounds emissions can occur and this technique
requires a high operation cost due to the need of an auxiliary fuel.
Absorption of carbon monoxide with copper salts solutions requires high pressures, around 300 ata. Nowadays, non-
aqueous solvents such as toluene with copper and aluminum chloride are used, since required pressures are between
30 and 40 ata [25]. Another option is adsorption of CO with molecular sieves, which are normally made of zeolites,
porous glass or aluminosilicate minerals. Since this technique is normally cheaper than polymeric membrane
separation and it does not require large equipment (compared to absorption and desorption columns), it has been
selected for CO removal in the process. Membranes do not work satisfactorily with high gas flowrates and need
usual changes because of obstruction, leading to high maintenance wastes.
8.3. H2 recovery
Hydrogen may be recovered from the purge stream of the first part of the process, methanol synthesis process,
where it is the most abundant waste gas. Another option is flaring, so that high temperature steam is produced for
usage in the plant or other applications. Hydrogen is a valuable commodity due to the increasing need for
hydroprocessing of feeds and products of refinery processes. Therefore, its recovery is economical and worth.
Several methods can be used: cryogenic distillation, absorption, adsorption and membrane separation. Cryogenic
distillation is energy intense because very low temperatures are required. By absorption, hydrogen is obtained at low
purity. Thus, adsorption and membrane separation are the preferred technologies for H2 recovery at present [12].
Adsorption processes can be carried out as a transient process before membrane separation. Since hydrogen is
practically unadsorbable, a purified gas stream containing it can be obtained, after impurities adsorption. High
pressures increase adsorption because it occurs in the small cavities of the adsorbent, where gases can pass faster if
pressure increases. For this reason, adsorbent can be later regenerated either by raising temperature (TSA) or
reducing pressure (PSA).
Membranes are usually made of polymers and their most important properties are high selectivity, high
permeability, high mechanical stability, thermal stability and chemical resistance. Permeability is also determined by
the membrane thickness. For this type of membranes, separation depends on solubility, which determines the
selectivity. Separation of
compounds is also based on molecular properties such as molecular size. Membrane, the selective barrier, would
allow some components to pass through in the permeate stream, and retain some others in the retentate stream.
Inorganic membranes (palladium, zeolites), which selectivity depends on adsorption properties and the pore size of
the surface, are gaining importance nowadays [12]. Advantages and disadvantages of membranes are shown below:
Table 51. Advantages and disadvantages of membranes [12]
Fouling consists of blocking of the membranes course and is one of the largest problems of these materials. Some
solutions are changing the surface characteristics of the membrane or decreasing the concentration of materials
passing through it. Another disadvantage is that membranes do not exhibit a favorable economy of scale as for each
application special ones are required. Nevertheless, membranes are widely used in the separation of purge streams
because corrosive gases are usually present in these streams. Corrosion increases with moving parts of equipment,
which does not occur by using membranes.
Therefore, the most suitable treatment depends a lot on economics, which must be studied in a real case. That will
determine the best option between recovery and flaring. For hydrogen recovery from methanol synthesis process,
membrane separation technique has been selected. Despite the described problems of operation, high selectivity
membranes should be used for a good performance separation of this gas. The decision of material and type of
membrane relies on economic issues and yield for a specific real case.
8.4. CH4 removal
Methane is a strong greenhouse effect gas, which contributes to the Earth global warming. Since CH4/air mixtures
are explosive and this is an extremely flammable gas, it must be removed from purge stream of methanol synthesis
(molar compos. 1,48 %), before gas release to the atmosphere. In the second part of the process, a negligible amount
of methane exits, according to methane average concentration in the atmosphere. There is not a limit emission value
for methane determined by environmental regulations.
Methane may be removed by flaring or catalytic combustion, which can lead to toxic gases formation like CO and
requires an auxiliary fuel, as already mentioned. Another method is membrane separation, but it is not an
economical option regarding membranes disadvantages and maintenance costs; this high inversion is not worth for
methane removal. Other options such as absorption may be used. Mineral oils are good absorbents for volatile
hydrocarbons and spray towers are the simplest and most economical columns. They exhibit low pressure
drop and are efficient when the hydrocarbon is highly soluble in the absorbent, the mineral oil [24]. Last option has
been selected for removal of methane from first exiting gas stream, which contains 198,14 kg/h of this gas. 8.5.
CH3OH removal In the second and last part of the process, purge stream mainly contains unreacted methanol (93,3
%), a certain amount of carbon dioxide, carbon monoxide, very low amounts of hydrogen and methane. Therefore,
apart from other gases already mentioned, methanol must be removed from this purge stream due to its potential
dangers for the environment. Methanol removal from gas stream can be performed by absorption with water,
biofiltration or by adsorption with molecular sieves, bleaching earth or silica gel. Although biofiltration is a low cost
technique, it generates residues, requires big space and is preferable for large volumes of gases with low
concentration of the organic compound (<2000 ppm) [24]. Depending on the efficiency and price of the available
adsorbent, this technique may be selected instead of absorption. Both methods could be used for methane
elimination in the process, and real parameters and factors determine the election. 8.6. Waste water treatment
According to the Industrial Emissions Directive 2010/75/EU, main pollutants to consider in waste water streams are
shown below [22]:
1. Organohalogen compounds and substances which may generate these compounds in the aquatic environment 2.
Organophosphorus compounds 3. Organotin compounds 4. Substances and mixtures with proved carcinogenic,
mutagenic properties or which may affect reproduction via aquatic environment. 5. Persistent hydrocarbons and
persistent, bioaccumulative toxic organic substances. 6. Cyanides 7. Metals and their compounds 8. Arsenic and its
compounds 9. Biocides and plant protection products 10. Materials in suspension 11. Substances which contribute to
eutrophication (in particular nitrates and phosphates) 12. Substances which have an unfavorable influence on the
oxygen balance (and can be measured using parameters such as BOD, COD, etc.) 13. Substances listed in Annex X
of Directive 2000/60 / EC.
Waste water streams from distillation columns T-101 and T-202 must be treated before release to the rivers.
According to the reference environmental normative, limit emission values (LEV) for chemical sector are shown in
the table:
Table 52. Limit emission values for waste water streams [26]
Waste water streams mainly contain methanol and other organic compounds, in higher concentration than the
allowed emission values. There are not suspended solids or other harmful chemicals; only biological treatment is
needed for purification of effluents in order to meet environmental requirements.
Since the most abundant organic compound in both waste streams is methanol, it has been used for calculation of
BOD parameter. Remaining organic content has been neglected. Stream 22, which exits column T-101, has a
methanol mole fraction of 0,0047. With this, average BOD is calculated as 35 g/L. Stream 36, exiting T-202, has a
methanol mole fraction of 0,0131. Estimated BOD is 12,5 mg/L for this stream. Therefore, total average BOD is
obtained as 47,5 mg/L. Biological treatment would consist of an anaerobic step followed by an aerobic treatment.
Parameter Value BOD5 1 g/L COD 1,6 g/L Oils 0,1 g/L Sulfides 0,002 g/L pH 6-9
9. SAFETY
Occupational health and safety assurance must be also considered in the process. Possible hazards and suitable
precautions are explained for manipulation of every chemical compound.
9.1. Process materials
Materials generated, consumed and released during the process have been considered in terms of: specific health
hazards, fire-fighting measures, accidental release measures and precautions.
9.1.1. Safety considerations for methanol
A small amount of methanol is found in the product stream. It is a volatile and flammable liquid that is mixed well
with air, easily forming explosive mixtures. It is miscible with water, alcohols, esters, ketones and most organic
solvents.
Health hazards of methanol are listed below:
 Methanol vapor and solutions are irritating to the skin and eyes.  Skin contact can cause dryness, cracking and
dermatitis.  Methanol is well absorbed by inhalation, oral and percutaneous routes and can cause metabolic acidosis
and damage to the central nervous system, optic nerve, retina and liver.
In order to prevent health hazards, the following should be done:
 Gloves must be worn for protection of skin.  Chemical goggles must be used.
Methanol is highly flammable and burns with an invisible or light blue flame. It may be ignited by heat, sparks or
flames. In order to prevent fire hazards, the following should be done:
 Methanol must be used and stored in cool closed systems with ventilation and explosion-proof electrical
equipment and lighting.  Contact of methanol with oxidants must be avoided.  There must not be ignition sources
by the process equipment and facilities.
In case of fire, the following should be done:
 Small fires can be fought with dry chemicals or carbon dioxide water spray.  Large fires can be put off with water
spray, fog or alcohol-resistant foam. Water spray should be used to cool down containers in the fire area.
Safety
In case of release, the following should be done:
 Dangerous area must be evacuated.  Leaking liquid must be collected in sealable containers, or should be diked
far ahead of liquid spill for later disposal.  Spilled liquids must be flushed with copious amounts of water. 
Protective wear, appropriate to the degree of spillage, must be worn.  Extra personal protection can be achieved by
using complete protective clothing, including self-contained breathing device [27].
9.1.2. Safety considerations for dimethyl ether
Dimethyl ether is a highly flammable and slightly toxic gas. Its vapors are heavier than air. Any leak can be either
liquid or vapor.
Health hazards of dimethyl ether are shown below:
 Vapor can cause eye, nose and throat irritation.  Over exposure or asphyxiation.  Target organs are liver, central
nervous system, cardiovascular system, and respiratory system.  High exposure can cause anesthetic effects, as well
as headache, dizziness and even loss of consciousness.
 If there is eye contact, eyes must be flushed with plenty of water for at least 15 minutes.  If there is skin contact,
freezing may occur. The person must be flushed with lukewarm water; hot water should not be used.  If a large
amount is swallowed, medical attention is required.  Victim must be lead to fresh air, as quickly as possible.
Trained personnel should dispense supplemental oxygen and/or cardio-pulmonary resuscitation, if necessary.
Dimethyl ether has severe fire and explosion hazards. The hazardous combustion products are formaldehyde, oxides
of carbon and peroxides. In order to prevent fire hazards and in case of fire, the following should be done:
 Dimethyl ether fires must be extinguished by shutting off the source of the gas.  Recommended extinguishing
media are water spray, water fog, chemical drying or carbon dioxide.  Water must be applied from a safe distance
to cool container and protect surrounding area.  In a fire or if heated, a pressure increase will occur and the
container may burst, with the risk of a subsequent explosion.
 Firefighters should wear appropriate protective equipment and self-contained breathing device with a full-face
piece operated in positive pressure mode.
 It must not be released to the environment.  Uncontrolled releases must be responded to by trained personnel
using specific procedures.  Affected area must be isolated, and personal protective clothing and equipment should
be worn.  Heat, flames, sparks and other sources of ignition should be avoided [28].  Monitor the surrounding area
for combustible gas and oxygen levels.
9.1.3 Safety considerations for carbon monoxide
Carbon monoxide is a highly toxic, flammable gaseous oxide, which is highly poisonous and is sparingly soluble in
water. Health hazards of carbon monoxide are listed below:
 Depending on the concentration and duration of exposure, it may cause headache, drowsiness, dizziness,
excitation, rapid breathing, nausea, vomiting, hallucinations, confusion, angina, convulsions, and unconsciousness. 
It may be lethal if inhaled.  The target organs are lungs, blood, cardiovascular system and central nervous system. 
Skin and eye contact may cause development of blisters, frostbite or blurred vision.  In order to prevent health
hazards, the following should be done:  It must be used only with adequate and explosion-proof ventilation
equipment.  Engineering controls need to keep gas, vapor or dust concentrations below any lower explosive limits.
 Suitable personal protective equipment for the body must be selected based on the task being performed and the
risks involved. This must be approved by a specialist before handling carbon monoxide.  Safety eyewear and
chemical-resistant, waterproof gloves complying with an approved standard must be used when a risk assessment
indicates that exposure to the chemical must be avoided. In case of a large spill, self-contained breathing apparatus
must be used to avoid inhalation of carbon monoxide.
In order to prevent fire hazards and in case of fire, the following should be done:
 Possible extinguishing media are carbon dioxide, regular chemical drying, water spray, alcohol-resistant foam. 
Containers must be cooled with water spray until well after the fire is out.  Containers must be moved from the fire
area if this can be done without risk.  Containers must be protected from heat exposure, as otherwise they may
explode.
Safety
 All the staff must be evacuated from the danger area.  Atmosphere must be checked with an appropriate device. 
All sources of ignition must be removed.  The affected area must be well ventilated [29].
9.1.4. Safety considerations for carbon dioxide
Carbon dioxide is a colorless, odorless gaseous oxide, heavier than air and highly soluble in water. It is a major
component of flue gas and is usually stored in liquid phase, as a compressed liquefied gas. At very high
temperatures, it decomposes producing toxic carbon monoxide.
Health hazards of carbon dioxide are listed below:
 High concentrations in the air cause a deficiency of oxygen with the risk of unconsciousness or death. In a short-
term exposure, hyperventilation can also occur, and a rapid evaporation of the liquid may cause frostbite as well. 
Inhalation can cause dizziness, headache, tachycardia or elevated blood pressure.  After long-term exposure, it may
have effects on metabolism.  Skin and eye contact may cause frostbite on contact with liquid carbon dioxide.
 Checking oxygen content before entering exposure area.  Engineering controls need to keep gas below
decomposition temperature.  Suitable personal protective equipment for the body must be selected based on the
task being performed and the risks involved.  Safety goggles, chemical-resistant, cold-insulating gloves and
protective clothing must be used. In case of a large spill, self-contained breathing apparatus must be worn to avoid
inhalation of carbon dioxide.
Carbon dioxide is not combustible, but CO2 containers may burst in the heat of a fire. In this case, all extinguishing
agents are allowed and the following should be done:
 Cylinders must be cooled with water spray until well after the fire is out.  Containers must be protected from heat
exposure, as otherwise they may explode.

 All the staff must be evacuated from the danger area.  Atmosphere must be checked with an appropriate device
(checking O2 content).  All sources of ignition must be removed.
 Affected area must be well ventilated. When spillage disposal, never direct water jet on liquid carbon dioxide.
Staff must be protected with self-contained breathing apparatus [29].
9.1.5. Safety considerations for methane
Methane is a colorless extremely flammable gas, lighter than air and sparingly soluble in water.
Health hazards of methane are listed below:
 High concentrations in the air cause a deficiency of oxygen with the risk of unconsciousness or death. In a short-
term exposure, contact with compressed or liquid gas may cause frostbite.  Inhalation may cause suffocation and
unconsciousness. The gas can be absorbed into the body by inhalation.  Serious frostbite can occur on skin after
contact with liquid methane.
 Checking oxygen content before entering exposure area.  Suitable personal protective equipment for the body
must be selected based on the task being performed and the risks involved.  Chemical-resistant, cold-insulating
gloves and protective clothing must be used. In case of a large spill, evacuation is required. Specialized staff must
wear self-contained breathing apparatus to avoid inhalation and ventilation is also required.
In order to prevent fire hazards and in case of fire, the following should be done:
 As methane is a highly flammable gas, no flames, sparks or smoking are allowed in the surrounding area.
Extinguish fire with water spray, powder or carbon dioxide.  Closed system, ventilation and explosion-proof
electrical equipment are required.  Containers must be cooled with water spray until well after the fire is out.
 All the staff must be evacuated from the danger area.  Atmosphere must be checked with an appropriate device. 
All sources of ignition must be removed.  The affected area must be well ventilated [29].
9.1.6. Safety considerations for hydrogen
Hydrogen is a colorless, odorless, tasteless, flammable non-toxic gas. It is extremely flammable in the presence of
oxidizing gases, such as oxygen, fluorine or chlorine; it also
Safety
has an auto ignition temperature of 500 to 571°C. It burns with an invisible blue flame, which may cause localized
heating and explosion or rupture of pressure vessels.
Health hazards of hydrogen are listed below:

 In the absence of oxygen, it can be lethal.  Contact with rapidly expanding gas may cause burns or frostbite, and
can be irritating to exposed skin and eyes.  Hydrogen is a simple asphyxiant, which acts displacing oxygen in the
environment. Inhalation problems are due to lack of oxygen.  Moderate concentrations may cause headache,
drowsiness, dizziness, excess of salivation, vomiting, and unconsciousness.
 Personal protective equipment for the body must be selected based on the task being performed and the risks
involved and should be approved by a specialist before handling this product.  Insulated gloves are suitable for low
temperatures.  Splash goggles or safety glasses must be worn for protection from rapidly expanding gases.
In case of fire, the following should be done:
 Water should be applied from a safe distance to cool container and protect surrounding area.  If involved in fire,
shut off flow immediately if it can be done without risk.  Self-contained breathing device and usual protective gears
for firefighters are required.  Personnel must be evacuated, if necessary, to upwind area.
In order to prevent fire hazards, the following should be taken into account:
 It must not be in contact with open flames or electrostatic discharge.  It is flammable over a wide range of
concentrations in air.
 Protective equipment must be worn.  Leakage must be stopped without risk.  All non-essential personnel must be
evacuated.  Hydrogen rises and disburses rapidly; hence, the area must be ventilated and isolated until gas has
dispersed [30].
10. ECONOMIC ANALYSIS

The economic analysis of the process has been done regarding capital cost including the most important equipment,
and operating costs.
Capital Cost
In order to calculate the capital costs of all the equipment, the following expression has been applied in order to
obtain the purchase cost:
log10C 0 p = K1 + K2 log10 (A) + K3[log10(A)]2 ,
Where the capacity or size parameter, A, and the coefficients K1, K2 and K3 depend on the different equipment.
Correction factors for pressure might be also applied for calculation of bare module cost, CBM. Bare module factor
(FBM) is used for material correction and sometimes pressure [16].
- Heat exchangers and vessels: CBM = C0 pFBM = C0 p (B1 +B2FMFP)
- Compressors: CBM = C0 pFBM

- Distillation columns: CBM = C0 pNFBMFq [16]
Adequate factors are applied to bare module costs to obtain the final installation costs, depending on equipment and
material of construction, which is considered as stainless steel in all of them.
Table 53. Capital Cost summary
EQUIPMENT Purchased Equipment Cost (€) Bare Module Cost (€) Final installed Equipment Cost (€)
E-101 4991,1 29804,4 56628,4 E-102 4380,1 26156,3 49697 C-101 22776,6 132104,3 158525,2 C-102 44929,7
260592,2 312710,5 C-103 7265,4 42139 50566,7 R-101 15945,7 125827,3 239072 R-102 14595,3 115171,8
184274,9 R-201 65280,4 515127,5 875716,7 S-101 6838 53965 91740,5 T-101 136137,0 306091,2 642791,5 T-102
35811,4 97114,8 203941,2 T-201 70582,0 156947,4 329589,6 Other HE total Cost 159687,4 512682,3 769023,4
TOTAL 589220,1 2373723,5 3964277,4
Economic Analysis
Apart from the first two heat exchangers, which are shell and tube type, the total cost of the other 8 present in the
process is calculated as well and summarized in the last row of the previous table. Total cost of process equipment is
estimated as roughly 4 million euros. Additional costs such as piping, other required facilities in the plant or
engineering costs have not been considered here.
Operating costs:
In order to calculate the total cost of operation of the dimethyl ether synthesis process, raw material and utilities are
taken into account. Based on the working days, 8000 hours are considered per year.
Table 54. Raw material costs
Apart from the utilities used for the reactors, which were already described in table 6.21, boiler feed water is used in
the heat exchangers for cooling down the gas mixture in the compression loop, before methanol reactor. After this,
two other heaters (E-106 and E-107) are used again for cooling before purification section, by using cooling water.
Before DME reactor, two heaters (E201 and E-202) are used to increase temperature and evaporate the liquid
methanol. Medium pressure steam is used for the first one, whereas the second requires high pressure steam. At the
end, another heat exchanger cools down the reactor exit stream before separation of dimethyl ether in the distillation
column.
All these heat exchangers data are shown below and their costs are calculated as well.
Table 55. Utility usage and costs for Heat Exchangers
In the compressors, electricity is required as utility. Usage and costs for all the compressors are given in table 56.
Table 56. Utility usage and costs for Compressors
Natural Gas 0,025 8505,87 1695730,243 Low Pressure Steam 0,027 28654,56 6120614,016 Total Raw Material
Cost 7816344,259
Raw Material Cost (€/kg) Consumption (kg/h) Annual cost (€/year)

Utility type BFW BFW BFW CW CW MPS HPS CW Utility duty (kW) -46749,5 -15652,7 -9541,29 -17214,4 -
9830 428,7 5465 -4460 Utility usage (kg/h) 433688 145208 88513,1 2,97E+06 1,69E+06 758,5 11443 769074
Utility cost (€/h) 10,80 3,62 2,20 11,69 6,68 3,02 43,78 3,03
Equipment E-103 E-104 E-105 E-106 E-107 E-201 E-202 E-203
Utility type Electricity Electricity Electricity Utility usage (kW) 15652,7 9541,3 19277 Utility cost (€/h) 1079,65
658,11 1329,63
Equipment C-101 C-102 C-103
In the condensers and reboilers of the distillation columns, boiler feed water, cooling water and low or medium
pressure steam are used, depending on the required duty. Utility usage and costs for condenser and reboiler of DME
distillation tower are expressed in table 57:
Table 57. Utility usage and costs for condenser and reboiler of DME column
With all of this, the total utility cost can be calculated:
Table 58. Total Utility Cost
And now total operating cost can be obtained by adding total raw material cost and total utility cost. The result is
roughly 15 million €.
The sale price of DME has been found as 0,75€/kg [31]; with this, annual revenue may be obtained.
Table 59. DME annual revenue
Therefore, the project seems profitable according to the previous calculations for annual production. Annual revenue
is around 58 M€.
Utility type BFW MPS Utility duty (kW) -2897,5 498,6 Utility usage (kg/h) 623079 882,2 Utility cost (€/h) 15,53
3,51
Equipment Condenser Reboiler
Utility Name Cost (€/GJ) Consumption (GJ/h) Annual cost (€/year) Low Pressure Steam 1,69 57,3 775154,4
Medium Pressure Steam 1,96 3,34 52317,76
High Pressure Steam 2,22 19,7 349872
Boiler feed water 1,04 303,5 2528276,4 Cooling water 0,19 156,48 233968,896 Electricity 2,85 160,1 3647718,4
Total Utility Cost 7587307,856
Product Price (€/kg) Production (kg/year) Revenue (€/year) Dimethyl Ether 0,75 78622720,0 58778345,47
Social and professional responsibility

11. SOCIAL AND PROFESSIONAL RESPONSIBILITY

11.1. Social issues
Dimethyl ether is one of the best alternatives for diesel engines market in the near future, as well as a more friendly
fuel for multiple applications. In countries like China, where an enormous air pollution exists, it is already having a
great influence in society. Regarding this, several advantages of DME have been already explained for justification
of this project.
Apart from this, if this process is finally applied in a real plant, suitable precautions explained in “Safety” must be
considered. The plant would require several workers, technicians and engineers from several backgrounds, resulting
in a positive effect on society.
11.2. Environmental impacts
As mentioned in chapter 8, environmental considerations for DME synthesis plants rely on harmful gases emissions
and toxicity of waste water streams. Proper treatments of pollutants exiting this process have been already described.
The atmospheric composition has always been in constant evolution. The problem is that during the last 100 years,
CO2 amount has increased in 25 % and CH4 amount has doubled. These gases alter the radiative equilibria of
atmosphere, and is it known that this increase is generating an accelerated atmospheric warming [24].
Dimethyl ether can cause big damage in animal life. Clinical trials on animals have shown anesthesia, which may
indicate possible harmful effects on central nervous system, liver and cardiovascular system. There is no evidence of
harmful effects on aquatic life and plants.
Methanol is a potential harmful compound for both animals and plants. It can be decomposed by solution in other
similar organic compounds. Due to the high toxicity of these substances, especially methanol, dimethyl ether
production plants must have an independent drainage network for evacuation of each waste stream (waste water,
process fluids and so on).
11.3. Legal issues and ethical considerations
Applicable regulations regarding safety signs and occupational health must be all assessed and applied in a real
DME plant.
Employees should be warned from all the risks in the plant and prohibitions, as well as obligations. It must be easy
for workers to find and identify protective facilities and equipment. First aid kits must be always available and
updated, for emergency or evacuation situations.
12. CONCLUSION AND FUTURE PROSPECTIVE

After analysis of the process options, design and simulation of DME indirect synthesis from natural gas is performed
with Aspen Plus ® and the aim of this project has been achieved. DME has been obtained with a molar purity of
98,6 %, as it was determined. Results were obtained and some optimization was required in order to achieve the
target purity of the product. The capacity of the plant has been defined as 90000 tons/year, according to the current
demand of dimethyl ether. Battery limits defined for this process consider crude methane as the representative
compound for natural gas.
Operation conditions for reactors are researched and selected, regarding high and feasible conversion values. With
this basis, design specifications for all the equipment are defined. Separation units are determined by doing several
previous sensitivity analysis, in order to figure out the best conditions of temperature and pressure. Reflux ratio is
modified by using Design Specifications module in order to achieve the required purity for the product. After
simulation is completed and results are obtained and validated, process control is implemented. Strategies for each
equipment and operation have been analyzed and control loops defined, taking into account the global process
performance and the relationship between the different parts of the process. After this, P&I diagram has been drawn.
In order to decrease harmful gases emissions and avoid water pollution in the rivers, environmental treatment must
be done for the waste streams exiting this process. Available techniques have been described, not implemented, by
outstanding the most suitable and feasible ones, from both technical and economic points of view. Safety
considerations when manipulating compounds in DME synthesis plants are crucial and most important precautions
were explained.
Finally, capital and operating costs are calculated. Process equipment cost is around 4 million euro and operating
costs, which include both utility and raw material costs, are 15 million euro. The sale price of DME is 0,75 €/kg and
annual revenue is estimated in 58 M€. Hence the project would be profitable.
European Union established the objective for which renewable energy sources become the 10 % of the total energy
used in transportation for 2020. This means that DME production and marketing is probably increasing in the near
future, as well as biofuels and other alternatives. China leads the worldwide production and usage of DME. In 2010,
50 % of the methanol produced in the country was used for DME and MTBE synthesis, and gasoline mixtures.
As continuation of this project, waste treatment for purge streams and waste water streams may be simulated. Only
applicable techniques have been described in this report, but environmental practical analysis can be further done
with the design and implementation of separation equipment. Aspen Plus ® could be used for this, at least for some
of the treatments, such as absorption.
One of the most promising methods for syngas production in the near future is tri-reforming, where the heat
produced in an exothermic reaction is used to provide the necessary heat for an endothermic reforming reaction.
Thus, it is about to gain importance in DME production in terms

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The production of DME in Spain is mainly carried out by aerosol and fuel industry.

Due to its global increasing

Process design and control of DME synthesis

Laura Martín Méndez 15

16 Escuela Técnica Superior de Ingenieros Industriales (UPM)

Process design and control of DME synthesis

18 Escuela Técnica Superior de Ingenieros Industriales (UPM)

1) POWER PLANT FUEL

1. Road load test data. Engine emissions comparison [7]

Process design and control of DME synthesis

Laura Martín Méndez 19

4) HYDROGEN FOR FUEL CELLS

20 Escuela Técnica Superior de Ingenieros Industriales (UPM)

2. Evolution and development of DME markets and applications [4]

Process design and control of DME synthesis

Laura Martín Méndez 21

5. PROCESS OPTIONS AND SELECTION

5.1. Feedstock selection

Process options and selection

22 Escuela Técnica Superior de Ingenieros Industriales (UPM)

Natural gas as a feedstock:

5.2. Direct and indirect synthesis methods

2CO + 4H2 ↔ 2CH3OH ΔH298= -43,4 kcal/mol (1)

CO2+ 3H2 ↔ CH3OH+H2O ΔH298= -11,9 kcal/mol (2)

Subsequently, DME is produced by dehydration of methanol in the following reaction:

2CH3OH ↔ CH3OCH3 + H2O ΔH298= -5,6kcal/mol (3)

Laura Martín Méndez 23

2CO + 4H2 → 2CH3OH ΔH298= -43,4 kcal/mol (4)

2CH3OH → CH3OCH3 + H2O ΔH298= -5,6 kcal/mol (5)

CO + H2O → CO2 + H2 ΔH298= -9,8 kcal/mol (6) [3]

3CO + 3H2 → CH3OCH3 + CO2 ΔH298= -58,8 kcal/mol (7)

2CH4 + O2 + CO2→ 3CO + 3H2 + H2O (8)

Process options and selection

24 Escuela Técnica Superior de Ingenieros Industriales (UPM)

3. Block diagram of indirect synthesis of DME from natural gas

Process design and control of DME synthesis

Laura Martín Méndez 25

6. INDIRECT SYNTHESIS OF DME

4. Block diagram of DME indirect synthesis

6.1. Components physical properties

Table 1. Physical properties [10]

Methanol CH3OH 32.04 337.67 80.32 512.68 175.53 20.98

DENSITY OF LIQUID AT 25ºC (Kmol/m3 )

COMPONENT NAME FORMULA MOLECULAR WEIGHT (Kg/Kmol)

NORMAL BOILING POINT (K)

Indirect synthesis of DME

26 Escuela Técnica Superior de Ingenieros Industriales (UPM)

6.2. Reaction stoichiometry and kinetics

CH4 + H2O ↔ CO + 3H2 (9)

r =1,527 exp (-14,820/RT) ������������������4 1.014

r =1,527 exp (-14,830/RT) PCH4 PH2O (11)

Ea =14,82 kcal/g mol

k=1,527 g mol/gcat h [11]

CO+ H2O ↔ CO2+ H2 (12)

Next, synthesis gas experiments two reactions where methanol is produced.

CO + 2H2 ↔ CH3OH (14)

CO2+ 3H2 ↔ CH3OH+H2O (15)

Process design and control of DME synthesis

Laura Martín Méndez 27

Reaction kinetics is shown below [14]:

r =1,527 exp (-14,820/RT) ��4 1.014

r = �� 1.9��2 0.9

Ea=80,48kJ/mol; k=1,21*106 ��