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Petrochemical Processes: Topic: Metanol To Olefins

The document summarizes the methanol to olefins (MTO) process. 1) The MTO process converts methanol, which can be obtained from coal or natural gas, into light olefins like ethylene and propylene using acidic zeolite catalysts. 2) Key catalysts used are ZSM-5 and SAPO-34, with SAPO-34 providing more selective formation of light olefins over wider range of products from ZSM-5. 3) However, SAPO-34 suffers from more rapid deactivation than ZSM-5 due to coking from aromatics and heavy molecules unable to diffuse through its small pores.

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Long Nhật Phan
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71 views13 pages

Petrochemical Processes: Topic: Metanol To Olefins

The document summarizes the methanol to olefins (MTO) process. 1) The MTO process converts methanol, which can be obtained from coal or natural gas, into light olefins like ethylene and propylene using acidic zeolite catalysts. 2) Key catalysts used are ZSM-5 and SAPO-34, with SAPO-34 providing more selective formation of light olefins over wider range of products from ZSM-5. 3) However, SAPO-34 suffers from more rapid deactivation than ZSM-5 due to coking from aromatics and heavy molecules unable to diffuse through its small pores.

Uploaded by

Long Nhật Phan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Petrochemical Processes

Topic : Metanol to olefins

Supervisor:Prof.Pham Thanh Huyen


Team : Pham Duy Tung - 20175329
Phan Long Nhat- 20175031
Nguyen Thanh Tu-20175315
Nguyen Van Anh- 20174391 1
I.Overview of MTO process
• The MTO process was first reported in the early 1970s by Mobil Company.
• The methanol can first be obtained from coal or natural gas.
• In the Methanol to Olefins (MTO) process, the methanol is then converted to
olefins such as ethylene and propylene.

Process flow diagram for an MTO process advertised by Honeywell Corporation


2
II. Resources & Application
• MTO using natural gas,coal or biomass raw material, is an
important alternative to oil-based routes for the production of
ethene and propene.
• Have been widely used as important raw materials for various
chemicals in the chemical industry.
• MTO process has proven to be a successful non-petrochemical
route for the production of light olefins from abundant nonoil
resources, such as natural gas, coal, and even biomass using
methanol as the intermediate.

Polyolefin plastic containers (right) and


shrink film (left)

3
III. Overview of MTO mechanism
• The conversion of methanol to olefins on acidic zeolites takes place
through a complex network of chemical reactions.
• The distribution of products and thus the “selectivity” depends on the
temperature, among other factors.
• In general, at lower temperatures methanol reacts to form dimethyl ether (DME).
At higher temperatures, the desired products (olefins) are produced and the
selectivity for DME decreases.

Percent conversion and yield at steady-state for


methanol conversion on H-SAPO-34 4
IV. Order Of Process
• Coal-Syngas-Methanol-Olefins
1, Coal to syngas 2, Syngas to Methanol

T=350oC

H2/CO=1/2.25

Syngas is synthesized from coal. It is a mixture In high pressure and moderate temperature
of carbon monoxide (63% by volume) and condition syngas (CO and H2) converts to
hydrogen (27% by volume) Methanol as following reaction:
CO + 2H2 = CH3OH
Besides, side reactions are:
CO + H2 = CH4 + CO2
CO + H2 = CH4 + H2O 5
3, MTO process

Main Reactions: 2CH3 OH = C2H4 +2H2O


3CH3 OH = C3H6 +3H2O
The formation of DME takes place according to the following steps:
1. Reversible adsorption of methanol molecules on the Bronsted acid sites of
the SAPO-34.
2. Dehydration of the protonated methanol tform the surface methoxy.
3. Reaction of gas phase methanol with the surface methoxy group to form a
surface associated dimethyloxonium ion (DMO+) 4. Formation of DME by the
deprotonation of the DMO+.

6
3, MTO process
• Two experiment were conduct with two feedstock: with iso-butene and
without iso-butene.
A.MTO by UOP

Diagrams of MTO process MTO process by UOP

7
3, MTO process
B, S-MTO by Sinopec C, D-MTO by Dalian Institute of Chemical Physics

8
3, MTO process
C, D-MTO by Dalian Institute of Chemical Physics

• The MTO research in DICP started since 1982 as a project supported


by Chinese government
• ZSM-5 as a catalyst for fixed-bed
• With ethene selectivity of around 30% or higher and propene
selectivity of 50%–60%, the simulation was based on the model
developed by DICP , the total conversion of methanol is limited to
90% to avoid the production of paraffins and aromatics. Also the
temperature is not supposed to exceed 500°C, as higher
temperatures would destroy the catalyst.
• ZSM-5 deactivates much slower than SAPO-34. 9
V.Catalyst
• Among all the investigated zeolites, ZSM-5 and SAPO-34
have received a lot of attention due to their excellent
catalytic performance for the MTO reaction.
• Unfortunately the use of ZSM-5 zeolite results in a wide
range of products, in particular aromatics and paraffins.
• The use of small pore zeolites and in particular SAPO-34
permits the selective formation of light olefins even at 100%
methanol conversion.

10
Product yield comparison between SAPO-34 and ZSM-5
V.Catalyst
1, ZSM-5 2, SAPO-34 (Silicoaluminophosphate)
• The structure of ZSM-5 contains two • SAPO-34 has the chabazite like structure.
perpendicularly intersecting channel
systems

Structure of ZSM-5 Structure of SAPO-34

11
3. Catalyst Deactivation
• Compared to ZSM-5, SAPO-34 suffers from rapid
deactivation during methanol conversion.
• Deactivation starts when aromatics and heavy
branched compounds are formed inside the large
cages.
• These molecules cannot diffuse through the porous
structure of the SAPO-34 because their kinetic
diameter is larger than the pore-opening size.
• Thus, they remain inside the big cages where they
can coke.

12
3. Catalyst Deactivation
• The C6+ products can not be observed at the exit of the
reactor, but their rate of formation and concentration inside
the cages.

• Possible to suppress the steps that involve coke formation


on SAPO-34 by increasing the temperature and the water
content in the feed7ư

13

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