Introduction

“ As a promising and clean alternative, dimethyl ether (DME) has received increasing

attention Diesel fuel due to its high cetin, low automatic temperature and low pollutant

emissions. In order to produce a number of platform chemicals, DME also is an important

feedstock, including lower olefines, methyl acetity and formaldehyde”. Production of DME,

methanoleic Solid acid catalysts and transformation in the syngas dehydration as intermediate,

there were two important synthetic pathways have so far been developed to produce two phases

methanol. The DME synthesis is traditionally achieved by the use of various solid acid catalysts

like G-Al-2O3 and ( H - ZSM-5,H - Y and H - ZSM-22) acidified zeolites ;considered to be

The most advanced route and commonly Available in the chemical industry. Because of its low

cost and acidity, G-Al2O3 is the greatest. commonly catalyst used. However, their low activity

and its hydrothermal stability limit the catalyst performance and life of the g-Al2O 3 catalyser.

H-ZSM-5 among the zeolites is by its high catalytic performance und stability, the most widely

studied acid catalyst. Its bronze acidity is strong., it can however be easily made with the DME

synthesis that significant Side Product quantities, like Coke and even hydrocarbons. As a result

of coke formation or water presence, H - ZSM-5 catalytic activity is quickly declining. In

addition, methanol dehydration is balanced by DME [ Eq.1]. Catalytic reactor in a classic fixed

bed.

Equation 1

2𝐶𝐻3 𝑂𝐻 ⥦ 𝐶𝐻3 𝑂𝐶𝐻3 + 𝐻2 𝑂

∆𝐻 = −23.4𝐾𝐽 𝑚𝑜𝑙 −1
 DME from methanol usually depends on the catalyst's inherent activity and process

conditions, and on their productivity and DME selectivity. Therefore, new simultaneous

strategies increase methanol dehydration Conversion and selection to DME continue to be an

important challenge. In the last two decades of the intensification process through combining

catalytic and molecular sieving in a single device, the focus on the selective removal of one or

more product on site during a reaction is on the increase, to overcome a balance limit, thereby

increasing conversion.. Within the last two decades, CMRs are becoming increasingly

important. Taking into account Eq DME dehydration. (1) It is expected that the balance limit

will be eliminated by the Le ChatelierQs the principle if water is to be removed selectively

from the reaction system and thereby increase methanol dehydration to Dme conversion and

selectivity. In the course of methanol dehydration, several efforts have been made to use

hydrophilic membranes to remove water on the spot. Fedosov et al. could increase the

conversion of methanol from an 8% membransometrane-free conversion by 2,08C to 88% via

membrane-support The LTA membrane reactor zeolite is used. Lee et al, said that the water

was removed by an alumina silica membrane, the DME yield was increasing from 68 % to 83

%percent. An alumina silica membrane to extract water in situ can also be used in a separate

report for converting methanol from 80 percent to 86 percent.

In summarizing products with growing concerns about climate change, depletion of fossil

fuels, the global community has been encouraged to explore clean alternative fuels and energy

demand also reduce emissions of greenhouse gasses by increasing CO2. In the catalytic process

of syngas better methods have been developed to reduce CO2 efficiently to dimethyl ether

(DME). DME may be used mainly in a wide A range of solvent, aerosol propellant and

domestic fuel applications. The basic use of DME in compressive ignition engines as a possible
diesel substitute. Because of the low self - alignment temperature and the large cean count.

Moreover, because carbon dioxide is not connected and DME uses about 35 percent oxygen as

a combustion product CO2 emissions are lower. DME synthesis methods, depending on the

type of raw material, Mainly as direct and indirect are categorized. Methanol is generated

indirectly from methanol and then purified into DME syngas. By combining methanol

synthesis and dehydration, DME can be produced directly. The two steps are conducted

simultaneously in one single reactor using two-function catalysts. The preferred route for large-

scope production from a cost-and production point DME synthesis from syngas is direct in

comparison to both methods. DME synthesis has been suggested for strengthening innovative

multifunctional reactors in recent years. Heat exchangers, membrane reactors and reactive

distillation promise great improvements to chemical processes. The optimal gas and reactive

DME process design was proposed by Bildea et al. In terms of energy efficiency and lower

investment costs compare to traditional processes, the proposed process demonstrated

improved performance. This procedure is used for DME synthesis indirectly, which makes a

completely different process of syngas methanol necessary. The 2-stage model for the new

fluidised cloth and tube sheet membraner was developed by Mardanpour et al. and it was shown

that hydrogen penetration might increase the DME and CO production. In exothermal and

reversible reactions, they considered a constant temperature in the bed unacceptable. Catalytic

dehydration is a two - armed reactor, DME and catalytic cyclohexane-benzene

dehydrogenation, in Farsi, etc. During these investigations, an integral reactor was established.

This reactor has made considerable improvements, which include reducing the reactor size,

changing the thermodynamic balance and autothermality of the reactor Despite a favourable

temperature profile, this process still meets the conversion limits of the fixed bed reactors. In

synthesis with DME, Omata etal. developed a small-scale reactor, which shows a much higher

efficiency than the isothermal reactor. Other work,by using a neuro-artificial network and
network search, optimized TGR temperature settings and found the combination of high

temperatures on bed entry and low temperatures on bed entry was beneficial. The reaction

balance can also be overcome by removing water on the spot in membrane reactors. In order

to ensure the best rate of entry and water disposal, Irananshahi et al. proposed a method for

optimizing a reactor länge in 20 segments. In practicethese optimal profiles are hard to get. The

desired temperature profile can be achieved in the dual reactor configuration consisting of two

reactors operating under different conditions. Rahimpour suggested this configuration for the

production of methanol in the conversion section of the High temperature reactor first the

second reactor synthesis of methanol at low temperatures. In order to overcome the limitations

of the reaction balance, Vakili and Eslamloueyan have developed 2 industrial reactor types

Comprised of two reactors in fixed bed. They have developed and in a one - dimensional model,

maximized DME outlet mole fraction. The proposed optimal reactor depends on its results can

increase the DME output to sixty tons per one day in comparison with the standard process.

The current study is focused on the presentation, taking into account the significant benefits of

the configuration, of an industrial reactor with two reactor fluidised for direct DME synthesis.

Because of its lowest mass transmission resistance, and the better thermal remove, good

temperature and high conversion control, fluidized beds are superior to stationary beds. A

fluidized bed reactor of two types was modelled under the Traditional DME synthesis working

conditions (TOPSOE process). Working conditions an evolutionary (DE) difference is also

used to improve the desired production rate to achieve the most advantageous operational

conditions.
 1. Conversion of Methanol to DME

Methanol is then transformed into DME, water, and the Na-LTA hydrophilic zeolite

membranes into the H-FAU membrane shown in Figure 1. But a DME is not possible with the
“

Zeolite LTA membrane because the kinetical diameter of Dme exceeds the pores of the Na-

LTA membrane (about 0.4 nm), so both the reaction process and the separation process can be

carried out in one single reactor . The reaction on the product side should be shifted due to the
”

selective and continuous removal of the produced water and production of DMEs should

significantly increase. In addition, water from the reaction system could be removed

continuously to prevent deactivation of catalysts and the formation of secondary products

during DME synthesis.

Figure 1 dehydration of methanol to DME by in situ water removal

This FAU-LTA membrane was prepared with a porous a-Al2O3 tube with a covalent
“ ”

APTES (Aminopropyltrietaxylane) connector from Zeolite LTA to the Al2O3 base. FESEM

pictures show a zeolite LTA membrane on an APTES al2O3 tube in figures 2a, b. In good

coordination with earlier reports and without any cracks, tubers or other defects it has been
developed a well grown Zeolite LTA membrane with an width of approximately 4 mm with

APTES modified Al2O3 tubes. After a modification of the LTA-like-synectical zeolite and the

subsequent hydrothermal synthesis leading to zeolite FAU–LTA sandwich membranes on the

surface of a zeolite layer, the compact zeolite FAU was formed. (Figure 2 c and d)

performance in DME methanol dehydration of zeolite H-FAU / Na-LTA CMR has then

been assessed. In contrast, zeolite powder of H-FAU performance has also been tested in CFR

during dehydration in DME. As illustrated in Fig 3, and the conversion methanol to DME in

CFR is fairly low, while the maximum methanol conversion in DME in existing jobs was just

9.5% at 3108C. This low conversion of methanol in CFR can be justified by two reasons: (1)

The reaction of methanol dehydration to DME is balanced, reducing water conversion to acid

catalytic pores and blocks of water. In contrast, with the increase of the reaction temperature

in the CMR, There has been significant improvement in methanol conversion to DME (Figure

3). The maximum conversion of methanol within the CMR to DME was 90.9% at 310 8C,

which in the CFR is significantly higher (9.5%)

. The thermodynamic balance limitation for DME dehydration in CMR can be removed

selectively and continuously using the hydrographic zeolite Na-LTA membrane for the reaction
system, significantly improving methanol transformation. The catalyst's stability is also

improved by removing the water produced locally and increasing the selectivity of DME

formation.

In addition, we found that the conversion from methanol to DME within a packaged reactor

(PBMR) was also comparatively low, and the maximum conversion was about 35.4% from

methanol to DME in the 3108C. The ideal performance of the CMR was confirmed by a

mathematical modelling. The DME level increases and methanols decrease, with a catalytic

response mostly occurring on the membrane surface, from the reactor chamber to the

membrane surface as illustrated in figure 3. The hydrophilic FAU and LTA membrane removed

the water quickly, there was virtually no water content. However, no DME or methanol

gradients in the PBMR were found, and only near the LTA membrane surface zeolite water

may be removed, causing a poor methanol conversion. DME was found to be the only product

when DME synthesis was performed at CMR even at high temperatures (3108C). suggesting

that the desired DME product was essentially 100% selective. There are well-known factors in

CFRs with acid catalysts likeHY, HZSM-5, heteropolyic acid, and MFI that can easily reduce

the selection and deactivation of the DME. Small quantities of side products are easily formed

in acidic CFRs. As Fig 4 shows, the conversion of Methanol and Selective DME after 60 hours
were nearly consistent and the entire test time was not accelerated. Methanol conversion to

CFR for H-Y has been reported to be rapidly decreasing from 87.5 (2 h) to 83.4 (7 h), 46.2 (10

h) and 19.0% (14 h), and hastened disactivation was observed after 7 hours at stream. The

presence of water damages catalysts ' activity. It is well known. The selective and continuous

removal of water generated from the reaction system has effectively prevented the disactivation

of the catalyst.
Literature review

Innovative clean fuels are Dimethyl ether (DME), because their features are similar to

LPGs (fluid petroleum gas). DME is currently primarily utilized as a spray cans propellant. A

dehydration reaction of methanol produces about 150,000 tons per year worldwide. It must be

produced in large quantities at low cost to utilize DME as a fuel. Since metanol is generated

by synthesis gas (hydrogen and carbon monoxide), the production of DME directly from

synthesization gas would be more efficient. DME direct synthesis process technique developed

from synthesis gas over the last 15 years. In order to diversify energy resources in future DME

could be a promising option, the transport and use of DME in Japan is extensively studied as

well as the technological process for production. The properties of DME are similar to LPG

and can be used in different sectors: household, transportation, electricity generation, etc. DME

can be produced by synthesizing gas from different resources, including natural gas, coal or

coal bed methane. Different usage technologies are being developed for DME. An innovative

process has been developed for the direct synthesis of DME from synthesis gas. A high

conversion and high DME selectivity were achieved in the new developed catalogue in a slurry

phase reactor. In 2002, the project of the demonstration plant (100 tons per day) started with

the support of the japanese government, after the pilot plant (5 tons / day) testing, for further

technical development to marketing. Three continuous testing operations with a duration of

two to three months were successfully performed in 2003 and 2004. Several process parameters

were achieved under very stable conditions targeted for ATR and DME synthesis. On the basis

of the data obtained, a commercial-scale project is being scale-up studies. .

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 2. Physical and chemical Properties

Dimethyl ether (DME) is the simplest ether with a chemical formula: CH3OCH3. DME is

a colourless, chemical stable gas that boils at an ambient temperature below 25.1C, and DME

is easily liquefied due to its pressure of around 0.6 MPa at 25C. It is so physical that DME can

be distributed, saved and similar to the properties of LPG. Use LPG handling technology and

facilities. A toxicity study with fluorocarbon substitution propellants confirmed that its toxicity

is extremely low, similar to LPG, below the level of methanol. DME is broken down in the

troposphere for several 10 hours and does not concern the effect of greenhouse and ozone

depletion. DME can be used as a new, clean fuel for diffrent areas; residential, transportation,

power generation, etc. DME's flames are blue visible. DME is equipped with a Wob index of

52 to 54, similar to that for natural gas (heat ratio, resistance to gas flow) and thus can be used

for DME natural gas cooking stoves without any modification. DME is almost the same as

natural gas for thermal efficiency and emission. DME Cetane is high, so it can be used as fuel

in diesel engines. DME has a much lower viscosity and a much lower lubricity than diesel fuel.

Changes to the fuel injection system are required in order to keep the fuel injection stable in

the engine cylinder. The DME diesel test showed that no black diesel (particular) exhaust fuel,
NOx emissions were significantly lower and that the calorie fuel consumption was the same as

that of diesel as shown in Figure 5.

Figure 2 DIESEL Fuel VS DME Exhaust Emissions

Several cars were modified to power DME and public road tests were performed

successfully. DME has a huge fuel potential of fuel cell automobiles in the future, since it is

easily transformed into hydrogen as methanol. Gas turbine testing with DME was successfully

conducted for power generation. Oil or coal-fired boiler combustion tests were carried out.

With almost the same thermal efficiency, emissions were greatly improved.

3. Characteristics of DME Synthesis Reaction and Synthesis Gas

“

Production ”

A newly developed autothermal reformer with a carbon cycle for the production of

synthesis gas from natural gas, a slurry reactor for easy control of the temperature thanks to the

highly efficient thermal heat convection and a newly designed catalytic system suitable for the
slurry phase of the reactor are the main features of this process. Figure 2 shows the DME natural

gas production block-flow diagram, which is being developed by direct synthetization process.

Figure 3 Direct Synthesis Process

 DME synthesis reaction and catalyst system

The reaction formulas and reaction heat concerning DME synthesis are as follows:

“Equation 2”

“Equation 3”

“Equation 4”

“Equation 5”
“Equation 6”

Formula (2) reactions synthesized DME in three steps, synthesized by gas synthesis

(H2, CO): reaction methanol (4), reaction to dehydration () and shift reactivity (6). Reactions

(4) and (5) are combined into reactions (3), if the reaction is slow. The overall response to the

methanol synthesis is exothermic and the reaction heat dominates. Figure 7 below shows the

balance conversion of synthesis gas for the two DME synthesis reactions (CO conversion plus

H2 conversion).

Figure 4 Equilibrium Conversion (260C,5MPa)

For methanol synthesis react as a function of the hydrogen / carbon monoxide relation

(H2/CO) of the gaseous synthesis, the Formula (2) and Formula (3) and Formula (4) formula.

In each reaction, the balance conversion reaches its peak, with H2/CO equivalent to a

stochiometric, i.e. H2/CO for Formula (2), and 2.0 equivalents for both Formula (3) and

Formula (4). For Formula (2), the maximum balance is much higher than for Formula (3) and

(4). The Formula (2) by-product is CO2, which is effectively produced at cooler temperatures

with very little water, separating the liquid product from the reacted gas. By producing CO2,

dissolving in manufactured DME can be removed. The by-produced water content in the
reactor effluent is so high for the Formula (3) that the liquid gas separator's temperature is not

less than that of the water freezing. The recycling gas DME content is very high. For the

balance conversion of DME synthesis and for the gas-liquid separation, it is clear that Formula

(2) reagates superior to the Formula (3) reaction. The main reaction, Formula (2) or Formula

(3) depends upon the catalyst characteristics. In the slurry phase reactor, a catalyst system

appropriate for the slurry phase reactor must be developed, as catalyst particles are surrounded

by a solvent. In fundamental research, the catalyst system has three functions (Methanol

synthesis, dehydration, water gas shifting), efficient to perform Formula reaction (2). Catalyst

production technology was also developed to allow for large-scale testing.

4. Methods of production

 Direct and Indirect production process

In industrial applications, the DME is produced from the syngas by means of two

different configurations:

one-step process

The DME is generated directly from syngas in one reactor during the one - stufled

production process, in which both methanol formation and methanol dehydration are

supported by a bifunctional catalyst, as follows:

Methanol formation:

Water-gas shift:
Methanol dehydration:

Overall reaction:

Syngas is generated via a natural gas steam reform or coal / petroleum contaminants
gasification, and a purification unit is needed after a DME synthesis reactor, to separate the
DME in a dual distillation stage from water and methanol. A one-stage diagram is provided in
the following figure 8.

Figure 5 one step process

two-steps process

The two (indirect) processes support the methanol formation of syngas and DME

methanol production in two separate reactors, which contain the specific catalysts (the first
based on copper, the second based on silica-alumina). The figure below shows this process '

block diagram.

Figure 6 Two-step process block diagram

 DME production from renewable energies

Renewable energy as biomass, solar and wind can be used to produce the reactants of the

DME synthesis process. This makes DME a liquid energy vector that can store renewable

energy in a high-energy, easy-to-use, high-density fuel. Biomass, agro-residue, forest residue,

as power crops. A gasifying process to generate a one-step or two-step synthesizing syngas

stream can be used, as shown below. In contrast, anaérobic digestion + pyrolysis may be

employed to generate the CO and H2 stream if the starting biomass consists of organic trash,

manure or sewage.
Figure 7 DME from renewable energy

The syngas hydrogen stream can be generated by an electrolyser, provided by electricity

produced as photovoltaics, wind farms and then mixed with CO / CO2 from renewable energy

plants. In the DME, renewable energies are so "stored," which can easily be distributed, stored

and used as liquid fuel, differently than hydrogen itself, which has a number of unresolved

distribution and storage problems. A conceptual layout for solar / biomass DME production is

presented in the following plan.

Figure 8 DME production from solar and biomass

  DME production as a CO2 valorisation process

Instead of syngas, a DME production process can provide a CO2-rich feedstock to turn

CO2 into a high-value added product. This process does not emit CO2, which is the main

greenhouse gas (GHG), but turns it into a burning fuel which re-emits carbon dioxide. This

configuration is less well developed than the traditional synthesis method, but there is a great

deal of research to improve its performance since both DME production and GHG emissions

can be reduced, reducing DME's carbon footprint. The presence of CO2 in the reactor

environment leads to two main problems: carbon-rich feedstock affects the active status of a

methanol catalytic system, decreasing formation rates of methanol CO2 stimulates the reverse

reaction of a water gas shift to produce H2O, and preventing the dehydration of methanol. New

catalysts for carbon-rich mixing, selective membranes that remove water and promote

methanol dehydration and DME production from the response environment have primarily

been developed for research. They are adapted for carbon conversion.

5. Reaction kinetics of the dual reactor

For DME production based on the Langmuir-Hinshelwood and Hougen-Watson

mechanism the kinetics represented by Nie et al. have been selected This model was

experimentally validated. The following are eight components: H2, CO, CO2, H2O, methanol,

DME, N2, and CH4. H2 and CO are the principal reactants and control of the reactor is

facilitated due to the presence of inert components which absorb part of the reaction heating.

The following four reactions are involved in three syntheses approaches to dimethyl ether,

namely CO hydrogenation, CO2 hydrogenation and CO and CO2 parallel hydrogenation:

Equation 7

Equation 8

Equation 9

Equation 10

The above reactions are not independent, and each reaction can be obtained from a

combination of the remaining three reactions. In this process, reactions 1, 3 and 4 were

considered for simulating the reactor behaviour.

Equation 11

Equation 12

Equation 13

Where
Equation 14
Equation 15

Equation 16

The kinetic parameters are given in Table 1.

Table 1Reaction kinetic parameters
 6. Applications

 Transportation

DME is one of the world's most promising automotive fuel alternatives for various ultra-

clean, renewables and low-carbon fuels. In diesel engines, gas engines (30% DME/70% LPG),

and gas turbines, DME is suitable as a fuel. There are only modest modifications to convert a

diesel engine to be used on DME, with heavy diesel engine powered DME vehicles developed

by engine manufacturers, including Nissan and Volvo. As a fuel for automobiles, DME's

performance shows several major advantages compared to petroleum-derived diesel:

• Ultra low exhaust emission

• No particles (PM), very low NOx, no SOx)

• Low CO2 emissions

• Low motor noise

• Hight fuel efficiency

• High well to wheel efficiency

• Thermal efficiency equivalent to diesel engine performance

Another important advantage is the reduction or the removal of particulate emissions, also

called soot or black smoke. Diesel engines running on a 100% DME were smoke-free and soot

was significantly reduced by motors using DME / diesel fuel mixing. A 55–60 high cetane

rating* (compared with approximately 45 for the diesel derived from petroleum) and a boiling

point of -25 ° C offer quick fuel-air mixing, a lower inflammation time and excellent cold

starting properties–two further key advantages for DME's fuel use.

  Cooking and heating

DME is available to be mixed with LPG (up to 20 %) for cooking and cooking at home

without altering the distribution networks or machineries. DME use is expected, especially in

portable fuel countries in the developing world, to increase substantially in domestic

applications, as DME use and blend are spread across the growing LPM market.

 Power generation

For electric power generation, DME has a performance comparable to natural gas and

manufacturers as fuel for use in their gas turbines, like General Electric and Hitachi and

Mitsubishi, have approved it. For medium-sized power stations, DME is an efficient alternative

to other energy sources, in particular in isolated or remote areas where the transportation of

natural gas is difficult and where the construction of regasification terminals for LNGs would

not be viable.
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