Design of Dimethyl Ether Synthesis Plant based on

Thermodynamic and Kinetic Simulation Study

Krishna Nimesh| CSIR-Indian Institute of Petroleum, Dehradun

M.TECH -
ADVANCED
PETROLEUM
SCIENCE AND
TECHNOLOGY
EVALUATION OF VARIOUS OPTIONS FOR THE
SYNTHESIS OF DIMETHYL ETHER USING
SIMULATIONS



Evaluation of Various Options for the Synthesis of
Dimethyl Ether Using Simulations


By
Krishna Nimesh

A Thesis submitted in partial fulfilment of the requirements for the degree of
Master of Technology
At
CSIR-Indian Institute of Petroleum, Dehradun

DECLARATION

This is to certify that the project entitled Evaluation of Various Options for the Synthesis
of Dimethyl Ether Using Simulations submitted by KRISHNA NIMESH, a student of
CSIR-IIP, Dehradun is the bonafide record of the students own work and has been carried
out under the supervision and guidance of Dr. S. M. Nanoti (HOD-Refinery Technological
Division, CSIR-IIP, Dehradun). It is being submitted for the Degree of Master of Technology
in Engineering in the Advanced Petroleum Science and Technology. It has not been
submitted before for any degree or examination in any other University.













--------------------------------------
(Dr. Sunil Kumar)
Scientist C (Modelling and Simulation Lab)
CSIR-Indian Institute of Petroleum
Dehradun-248007
--------------------------------------
(Dr. S. M. Nanoti)
Scientist G (Modelling and Simulation Lab)
HOD-Refinery Technological Division
CSIR-Indian Institute of Petroleum
Dehradun-248007
--------------------------------------
(Krishna Nimesh)
Trainee Scientist (PGRPE-2012)
Master of Technology (APST)
CSIR-Indian Institute of Petroleum
Dehradun-248007

Abstract

Dimethyl Ether is a clean and synthetic fuel. Because of its properties similar to that of liquid
fuels such as LPG, Diesel etc. it can be thought as a substitute or alternative fuel to these in
the near future. The objective of this project is to evaluate various synthesis routes for the
production of Dimethyl Ether and/or Methanol from natural gas with the aim of improving
energy efficiency and reduction in polluting emissions such as CO
2
footprints, NOx, SOx etc.
Depending upon the route, there are 2 types of DME production processes available in the
literature viz. 1-Step and 2-Step processes. In both the processes, production of syngas from
carbonaceous feed stocks (Natural Gas, Coal, Biomass etc.) is the common step. When DME
is synthesized from the produced syngas through Methanol Dehydration route, it is called 2-
step process and if DME is directly produced from syngas it will be a single step process.
Both the processes require catalyst for Methanol or DME production.
In this project firstly pre-eliminary steady state thermodynamic or equilibrium simulation has
been done for several proposed flowsheets for DME production in ASPEN-HYSYS V8.4.
Based on several performance parameters, one best possible flowsheet is chosen for which
detailed steady state kinetic simulation is done to find out its industrial feasibility in ASPEN
PLUS V8.4. Before these simulation studies, validation of each and every parameter of
simulation model for each step was done to maintain its precision and accuracy to be used for
the simulation of DME/Methanol synthesis.
Maximum yield of DME/Methanol is directly related to the composition of syngas generated
in the respective processes. The important parameters such as H2/CO ratio, (H2-
CO2)/(CO+CO2) or R-Value ratio, CO2 % in feed etc. along with temperature and pressure
will not only have greater impact on the yield, selectivity of DME/Methanol but also on the
economics of the whole plant. Proper syngas composition is the vital parameter for which the
suitable reforming processes are identified which are followed by the methanol synthesis
and/or methanol dehydration processes. Eight different reforming processes viz. SMR, ATR,
SMR+ATR, Bi-Reforming, Tri-Reforming, POX+CO2 recycle and Dry Reforming has been
simulated using RGibbs reactor in Aspen Hysys V8.4 in thermodynamic study. These
reforming processes were chosen depending upon their suitability to produce specific
composition of syngas for the specified DME production Process. Combined reforming i.e.
SMR+ATR has been chosen for the final Kinetic study.
The steps such as Methanol synthesis and/or Methanol Dehydration are same in 1-step as
well as in 2-step processes. These have been simulated thermodynamically as well
kinetically. The 2-step DME synthesis process has been chosen along with SMR+ATR
reforming step as the final DME/Methanol Synthesis process. The specific DME production
rate for the given process is found out to be around 0.52 per kmol of methane. The specific

CO
2
footprint is around 0.63 while specific oxygen and water requirements are 0.8 and 0
respectively. The per pass conversion in the Combined Reformer, Methanol Reactor and
DME Reactor for the final flowsheet are found out to be 96.62, 63.32 and 84.59 %
respectively.
Pinch Analysis of whole process shows that the given process is a heat surplus process which
contains approx 1214 KW of extra heat. The process doesnt require any external hot utility
while the extra heat in the process can be used to produce HP steam of around 700 KW.



















Acknowledgement

I would like to thank and express my sincere gratitude to my guide Dr. S. M
Nanoti, HOD Refinery Technological Division, CSIR IIP, Dehradun for his
support, advice and positive attitude.
I am also very grateful to my co-guide Mr. Sunil Kumar, Scientist Modeling
and Simulation Lab for his participation in stimulating discussion and the time
he spent helping me. Without his support this project would have not been
possible.
I would also like to thank our Director, Dr. M.O. Garg for his kind support and
motivation he provided to me throughout the course of this project.
I will always be grateful to Dr. Sudip K. Ganguly, Dean PGRPE CSIR-IIP,
Dehradun for his invaluable guidance and advice.
Also I must express my gratitude to all scientists in the Modelling and
Simulation Lab for creating a supportive and friendly working environment.
I also feel a great pleasure to thank all the staff members of the Institute for their
cooperation and support which led to the successful completion of the project
work.
I also offer my regards and blessings to all of those who supported me in many
different ways during the period I spent working on this project.
Most importantly, I would like to thank my family: my parents, brothers and
sister for their support, encouragement and love throughout my life.





Table of Contents

Declaration
Abstract
Acknowledgement
List of Figures
List of Tables
Notations
List of Acronyms
Chapters
1. Introduction
1.1. D
1.2. F
1.3. F
1.4. F
2. Vdgf
2.1. G
2.2. G
2.3. G
3. Ff
3.1. H
3.2. H
3.3. H
4. Sd
4.1. F
4.2. F
4.3. F
5. Dgf
5.1. H
5.2. H
5.3. H




List of Figures
















List of Tables
















Notations
Abbreviations
Symbols Definitions Units










List of Acronyms















Chapter 1: I ntroduction and Objective

This thesis focuses on the Evaluation, validation and generation of flowsheet for the
DME/Methanol synthesis process to be used at industrial scale. In this chapter, an
introduction to Dimethyl Ether is given. The objective of the work is presented, and an
outline of the thesis is provided.
1. I ntroduction
With the increase in the modern technologies, life standard of people is also increasing day
by day. This advancement has dramatically increased the energy consumption all over the
world in the recent year. Fast growing developing countries such as India, China, and South
Africa etc. has shown rapid increase in terms of energy consumption. This rising energy
demand has shown a very steep decline in the present energy resources such as Petroleum,
Coal etc. Petroleum has been used for many purposes, either for energy or chemicals to
support modern society. However, we have consumed about half of the global reserves and
the remaining half is becoming increasingly expensive to exploit.
Figure-1: Energy Resource Consumption in India and World
[1]



Figure-2: Liquids (including biofuel, etc) consumption for India, based on data of US EIA,
together with Brent oil price in 2012 dollars, based on BP Statistical Review of World
Energy updated with EIA data
[2]


The sharp rise of the crude oil price Figure-2 comes from the close link between supply and
demand as well as the rapid increase in the oil consumption of several Asian countries. Also,
the energy situation is severe both in terms of the remaining resources and their impact on the
environment, as exemplified by the Kyoto protocol for global warming. In order to lessen
the environmental burden, it is strongly required to promote the more effective utilization or
the suppressed consumption of petroleum or coal. Hence there is a need of in-depth research
to develop sustainable clean technologies or processes which uses either renewable energy
resources or some other raw materials like Biomass, Natural Gas etc. instead of present fossil
fuels. These potential energy sources can be converted to different fuels having very high
calorific energy content. Such fuel will also contain fewer pollutants than that obtained from
petroleum or Coal. This is an advantage, because the cleaner the fuel is, the less damage it
can do to the environment. Well-known examples of technologies that convert carbonaceous
feed stocks to liquid fuel are the Fisher-Tropsch and Methanol synthesis processes in which
these feed stocks are first converted to Synthesis Gas (Syngas) which can be easily converted
into different liquid fuels such as Gasoline, Diesel, Methanol, DME etc.

Fig-4: Various Products from Synthesis Gas (Syngas)
[3]

Current fuels are more prone to emissions such as SOx, NOx, CO, CO
2
etc. which are
responsible for the environmental pollution so there is a need of research for such fuels which
can replace or can be used along with them with lesser polluting emissions. One such fuel
which is gaining large attention of all researchers all around the world is Dimethyl Ether
(DME). It is a clean colourless gaseous fuel that is easy to liquefy and can be transported
anywhere. It has a very great scope to be used as an alternative fuel, for electric power
generation and in domestic applications such as heating and cooling. It has never been used
as an energy material but it is now becoming a second promising synthetic fuel.
1.1 Why DME
As already mentioned DME is a clean gaseous fuel. It can be derived from many sources,
including renewable materials (biomass, waste and agricultural products) and fossil fuels
(natural gas and coal). It can be efficiently reformed to hydrogen at low temperatures, and
does not have large issues with toxicity, production, infrastructure, and transportation as do
various other fuels.
[4]
It is being used as a safe aerosol propellant which has replaced Current
Aerosols such as CFC gases which is also environmentally friendly.
[5]
It also has lower
possibility of producing carbonaceous particulate emissions as it contains oxygen and no
carbon-carbon bonds as Methanol. However, unlike methanol, DME has a high enough
cetane number hence it can be used as a clean high-efficiency compression ignition fuel with
reduced NOx, SOx, and particulate matter. Also unlike methanol, DME is a gas at ambient
temperature and pressure, so it must be stored under pressure as a liquid similar to LPG
(liquefied petroleum gas). DME provides reduced Particulate Matters and NOx emissions,
but increased CO and HC, when used as a diesel fuel.
[5]
Its vastly superior cold starting,
literally smokeless, quieter combustion, no fuel waxing in cold climates to clog fuel lines,

low NO
x
emissions, lower well-to-wheel greenhouse gas emissions than diesel fuel
[6]
, high
oxygen content, lack of sulfur or other noxious compounds, and ultra clean combustion and
potentially a CO
2
absorber in its production
5
makes it a versatile and promising solution in
the mixture of clean renewable and low-carbon fuels under consideration worldwide.
1.2 Background of DME production process
DME is produced by converting any carbonaceous feed stocks such as Natural gas, Coal or
Biomass into synthesis gas (syngas). The produces syngas is then converted into DME via 2
processes viz. 1-Step/Single Step DME Synthesis Process or Two-Step DME Synthesis
Process. In two step process, syngas is first converted to methanol in the presence of copper
based catalyst, and then by subsequent methanol dehydration in the presence of a different
catalyst such as -Alumina into DME. The following reactions occur:

CO + 2 H
2
CH
3
OH -181.6 kJ/DME-mol (1)
2 CH
3
OH CH
3
OCH
3
+ H
2
O -23.4 kJ/DME-mol (2)
CO + H
2
O CO
2
+H
2
-41.0 kJ/DME-mol (3)
Alternatively, in 1-step DME synthesis process syngas is directly converted to DME using a
dual-catalyst system which permits both methanol synthesis and dehydration in the same
process unit, with no intermediate methanol separation
[7]
. In this process, the intermediate
methanol synthesis stage is eliminated. Both the one-step and two- step processes are
commercially available. The reactions which are assumed to occur in single step process are
as follows:
3 CO + 3 H
2
CH
3
OCH
3
+ CO
2
-246.0 kJ/DME-mol (4)
2 CO + 4 H
2
CH
3
OCH
3
+ H
2
O -205.0 kJ/DME-mol (5)
In 1-step process also, reaction from 1 to 3 occurs, but the dual catalyst allows the synergy
between the reactions that allows higher syngas conversion per pass or greater productivity as
compared to the 2-step process
[8]
by consuming the intermediate Methanol as soon as it
produced. The synergy works in the following way: Methanol which is produced by reaction
(1) is consumed by Reaction (2). The water formed by Reaction (2) which would limit the
rate of Reaction (2) is consumed by Reaction (3). Reaction (3) generates hydrogen which
increases the rate of Reaction (1)
[8]
.

Though it has many advantages over 2-step process, but this process is not proven
industrially because of difficulties in the preparation of dual-functionalized catalyst which
has very complex mechanism. But this process has very great scope in the near future.

Several companies such as JFE
[9]
, Air Products and Chemical
[10]
, KOGAS
[11]
etc. have run
their plants on bench as well as on pilot scale and have shown very good performance.
On the other hand, 2-step DME process is well proven at commercial scale and several plants
has been running in various countries such as Japan, China etc. for several years. Various
Industries such as TOYO Engineering Corp.
[12]
, Mitsubishi Gas Chemical
[13]
, Lurgi
[14]
,
Uhde
[15]
, Haldor Topsoe
[16]
etc has their DME plants running successfully at industrial scale.
1.3 Objective
Although 2-step process is well proven, but still it has vast scope of advancement in many
areas such as catalysis, operating variables, heat integration, process intensification, reactor
designing, separation process etc. In the present work all these parameters are taken care of to
evaluate various 1-step and 2-step DME synthesis processes to find out the best suitable
process. Detailed kinetics study has been done for the selected process along with pinch
analysis to find out the external hot and/or cold utilities if any. Minimization of reforming
agents such as Water, Oxygen, CO
2
etc., Minimization of Refrigerants for cooling,
Miniaturization of process equipments, Minimization of external utilities, Maximization of
process to process heat transfer etc. are the main focus of the present work so that the
proposed flowsheet can be used in stranded areas at industrial scale.
1.4 Outline of Thesis
First general description and literature review regarding synthesis gas production from
Methane reforming processes along with Methanol synthesis and Dimethyl Ether synthesis
processes is discussed. The important areas such as Reaction mechanism, Kinetic Models,
Reaction parameters, Catalyst etc have been discussed in detail for every process. Steady
State thermodynamic simulation has been done for the various processes and the parameters
depending upon which the best process is selected is discussed in brief. Steady state Kinetic
simulation has been done for the selected process along with pinch analysis to get the better
insight of heat integration.







Chapter 2: Literature Review
Methane Reforming Process
Methanol Synthesis Processes
Dimethyl Ether Synthesis Process

2. I ntroduction
The relationships between various parameters in any process and effect of process conditions
(i.e. reaction temperatures, pressures and compositions etc.) on the possible product
distributions can be easily determined by doing thermodynamic and kinetic studies prior to any
scale up. To get the better insight of the overall process reactor designing is done based on
kinetic studies so that it can be modified for optimum operating conditions and better yields.
It is necessary to have a detailed knowledge of the reaction mechanism which can lead to the
generation of very efficient process which results in appreciable profits. One such industrially
important process is the Dimethyl Ether synthesis process. As a whole this process itself
consists of 2 or 3 sub processes Viz. Syngas Production, Methanol Synthesis and Methanol
Dehydration or Dimethyl Ether synthesis depending upon the route through which it is
synthesized. An extensive research has already been done on all these processes by many
researchers in terms of operating conditions, reaction mechanisms, reactor designing,
catalysts etc. for many years.
2.1 Synthesis Gas Production
Synthesis gas or syngas, is an important intermediate step in many existing and emerging
energy conversion technologies such as XTL (X=Coal, Biomass, Natural Gas), Methanol,
Dimethyl Ether etc. Several processes are available in the literature which can be used to
produce syngas
[17-26]
. Among all these processes Natural gas reforming is gaining more
attraction worldwide. It is also known as Methane reforming as it contains more than 80 % of
methane
[27, 28]
. Methane reforming can be performed by different techniques, each of which
has their own advantages and disadvantages. The product of natural gas reforming is a
mixture of gases known as syngas (Mainly CO and H
2
)
[29]
.
The composition of Natural gas varies region to region. It mainly composed of saturated
hydrocarbons such as methane in high percentage and higher hydrocarbons such as propane
and butane in lower quantities. In raw state, it also contains varied levels of impurities such as

nitrogen, carbon dioxide, water and sulphur compounds etc.
[29]
. Today natural gas is the
preferred source for production of syngas, a mixture of hydrogen and carbon monoxide, from which
purified hydrogen can be obtained. There are several different catalytic and/or thermal processes
for producing syngas from natural gas
[30]
. The classification is as follows:
1. Catalytic Natural gas Reforming:
a. Steam Methane Reforming (SMR)
b. Dry Methane Reforming (DMR)
c. Catalytic Partial Oxidation of Methane (CPOX)
2. Thermal Natural Gas Reforming
a. Partial Oxidation of Methane (POXM)
Other reforming technologies are the combination of above reforming processes which are as
follows:
1. Bi-Reforming of Methane: SMR+DMR
2. Tri-Reforming of Methane: SMR+DME+POX
3. Autothermal Reforming of Methane: POX+SMR
All these types of processes have the same objective and lead to same final product i.e. synthesis
gas.
2.1.1 Steam Methane Reforming (SMR)
Steam reforming is a well proven efficient process used mainly for the production of
hydrogen and has been in practice since 1930
[31]
. Standard Oil Co., USA began the first
steam reforming plant in 1930 with light alkanes as feed
[32]






Chapter 3: Flow sheet Development


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