VIET NAM OIL AND GAS GROUP

PETROVIETNAM UNIVERSITY

SEMINAR
METHANOL SYNTHESIS
FROM SYNGAS
Subject: Lubricant and liquid fuel
production process
Class: K5 LHD
Full name: Nguyễn Đình Anh
Ma Đức Hiếu
H Như Ý Byă
 Contents

A INTRODUCTION

B PROCESS VARIABLES

C PROCESS TECHNOLOGIES

D CONCLUSION

2
 A- Introduction

I- METHANOL

II- SYNGAS

III- PRODUCTION OF METHANOL

FROM SYNGAS

IV- BLOCK FLOW DIAGRAM

3
 1- Introduction of methanol

*What is methanol ?

Methanol is one of liquid fuel and it is a simple alcohol with the formula
CH3OH. It uses as fuel, solvent and feedstock for the generation of other
chemicals.

Figure A-1. Formula of methanol

4
 2- Methanol demands

Figure A-2. Methanol Demands and End Use in 2017. DMT: dimethyl
terephthalate, MTBE/TAME: methyl tert-butyl ether/tert-amyl methyl ether,
MTO: methanol-to-olefins, MTP: methanol-to-propylene.

5
 3- Feed stock of methanol production

Syngas Coal

Main source to
produce methanol
insist of: CO and H2

Higher
hidrocarbo Biomass
n

6
 A- Introduction

I- METHANOL

II- SYNGAS

III- PRODUCTION OF METHANOL

FROM SYNGAS

IV- BLOCK FLOW DIAGRAM

7
 II- Introduction of syngas
*What is syngas ?
Syngas (synthesis gas) is a mixture comprising of CO and H2 at any
ratio, is a crucial intermediate resource for production of hydrogen,
ammonia, methanol, synthetic hydrocarbon fuels - is also used in
producing synthetic petroleum for use as a fuel or lubricant.

Figure A-3. Introduction of methanol

8
 2- Syngas production

 There are five main

sources to produce
syngas

Figure A-4. Main sources of Figure A-5. Tri-reforming of natural

production of methanol gas using flue gas from fossil fuel-
based power plants.

9
 3- Uses of syngas and methanol and their conversion catalysts

Figure A-6. Examples of uses of syngas and methanol and their conversion catalysts.

10
 A- Introduction

I- METHANOL

II- SYNGAS

III- PRODUCTION OF METHANOL

FROM SYNGAS

IV- BLOCK FLOW DIAGRAM

11
 1- Characteristics of reaction

(3)

• Exothermic & endothermic reaction.

1
• To simplify, it can be considered that: (1) and (3)
2 is independent reaction, and (2) = (1) + (3).

• The total reaction is an exothermic reaction.

3

12
 2. Condition of temperature & pressure

• As these reactions are exothermic and lead to a

decrease of the amount of molecules present, the
T&P productivity can be increased by increasing pressure
and reducing temperature.

High pressure: 25 – 30 MPa

Pressure Medium pressure: 10-25 MPa
Low pressure: 5-10 MPa

Low pressure allow low capital investment, low production

cost leads to low product price and brings high flexibility in
choosing plant size

13
 3- Catalytic

 Catalysts for methanol synthesis was firstly used in 1996 by ICI

company (Imperial Chemical industry).
 Catalysts containing Cu have higher activity and selectivity than
ZnO or Cr2O3 catalysts.

 Most of methanol production technologies use heterogenous

catalysts based on Cu-ZnO-Al2O3.
 The nature of these catalyst in industry scale is still studied.
 Catalysts’ average industrial lifetime of 2-5 years

05/11/2020 14
 3- Catalytic

Table A-1. Metal composition of catalysts provided by different manufacturers

Manufacturer Cu at % Zn at % Al at % Other (at %)

IFP 45-70 15-35 4-20 Zr (2-18)

ICI 20-35 15-50 4-20 Mg

BASF 38.5 48.8 12.9  

Shell 71 24   Rare Earth Oxide

Sud Chemie 65 22 12  

Dupont 50 19 31  

United Catalysts 62 21 17  

Haldor Topsoe MK-121 >55 21-25 8-10  

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 A- Introduction

I- METHANOL

II- SYNGAS

III- PRODUCTION OF METHANOL

FROM SYNGAS

IV- BLOCK FLOW DIAGRAM

16
 IV- Block flow diagram

Figure A-7. A block flow diagram showing the combined steam reforming for
methanol synthesis.
17
 IV- Block flow diagram

Figure A-8. A block flow diagram showing the combined reforming and
autothermal for methanol synthesis.

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 B. PROCESS VARIABLE

• Length and width of the

reactor
• Feed temperature of the
reactor
PROCESS
VARIABLES • Feed pressure of the
reactor

• CO:H2 ratio

19
 1. Length and Width

Figure B-1: Influence of the reactor’s Figure B-2: Influence of the reactor
diameter and volume for a single reactor volume distribution on the pressure drop

20
 1. Length and Width

 A smaller reactor leads to less conversion which in turn means a

smaller methanol yield, but it also means the investment costs for
the reactor will be less.
 A clear drop in production can be observed for similar volumes with
smaller diameters.
 This pressure drop increases for reactors with same volume but
smaller diameters.
 At a lower pressure, the equilibrium of the reaction moves towards
the left side of equations. This leads to a lower methanol output

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 2. Temperature and Pressure at Reactor Inlet

Figure B-3: Influence of feed pressure and Figure B-4: Influence of the operating
temperature on the output of a single pressure for various pressure drops
reactor (Dimensions: 3.5m length and 2m between the reactor inlet and the flash
diameter)
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 2. Temperature and Pressure at Reactor Inlet

Temperature
 Higher temperatures produce less methanol while lower temperatures
produce considerably less methanol for higher pressures (red line)
 Operating temperature is between 200 ∘C and 210 ∘C

Pressure
 Higher operating pressure the compressors require more energy
 At a lower pressure the reactor produces less methanol
 Production of methanol increases with increasing pressure
 The range of operating pressure is 5-10MPa

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 3. CO:H2 ratio

Which ratio CO : H2 is needed for methanol production?

The ratio CO : H2 is 1:2

Adjustment of CO : H2 is required because of that the ratio of

syngas from natural gas is approximately 1:3

o Add some amount of CO2 to reaction to reduce H2

o Use combination of steam reforming and autothermal

reforming

o Get CO : H2 is approximately 1 : 2.05

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 3. CO:H2 ratio

Figure B-5: A block flow diagram

showing the combined reforming
for methanol synthesis

25
 C. PROCESS TECHNOLOGIES

I. General processes
• Block flow diagram
• Reactor of synthesis processes
• Methanol production by one-step reforming
• Methanol production by combined reforming

II. License processes

• ICI's Low-Pressure methanol synthesis process 
• Lurgi MegaMethanol synthesis process

26
 1. Block flow diagram

Single
column
One-step Adiabatic
reforming reactors
2 columns
Boiling
Two-step
water
reforming
reactors
3 columns

Figure C-1. Block flow diagram of methanol production from natural gas

27
 1. Block flow diagram

1) Reactor;
2) Heat exchanger;
3) Cooler;
4) Separator;
5) Recycle compressor;
6) Fresh gas compressor

Figure C-2. Methanol synthesis

28
 2. Reactor of synthesis process
Boiling water
Adiabatic reactors
reactors

Figure C-3. Reaction path in reactor

The main difference between different methanol production
technologies is the type of reactor:
Adiabatic reactor and Isothermal reactor

29
3. Methanol production by one-step reforming

Figure C-4. Simplified flow diagram of methanol production

by one-step reforming
30
4. Methanol production by combined reforming

Figure C-5. Simplified flow diagram of methanol production by two-step reforming

31
 Comparison
Advantages of combined reforming
• The syngas produced by one-step
reforming will typically contain a
surplus of hydrogen of about 40%.
• Provides ability to adjust the
syngas to obtain the most suitable
composition (CO:H2 close to 1:2)
• The tubular reformer is operated at
low S/C ratio, low temperature and
high pressure
• Higher capacity of plants.

Figure C-6. Methanol Production using Combined Reforming

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 5. ICI’s Low-pressure process

Figure C-7. A schematic of ICI's Low-Pressure methanol synthesis process 

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 6. Lurgi MegaMethanol process

Figure C-8. Process scheme for the Lurgi MegaMethanol synthesis process
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 6. Lurgi MegaMethanol process
Equipments for Lurgi MegaMethanol synthesis process:
a) Turbine for synthesis gas and recycle compressor;
b) Synthesis gas compressor;
c) Trim heater;
d) Combined converter system;
e) Final cooler;
f) Methanol separator;
g) Recycle gas compressor;
h) Expansion vessel;
i) Light ends column;
j) Pure methanol pressure column;
k) Atmospheric methanol column.
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 6. Lurgi MegaMethanol process
• Two reactors: the water-
cooled reactor (BWR) and
a gas-cooled reactor
(GCR)
• Cooling gas of the GCR is
the unreacted syngas →
only a small preheater
required
• GCR is a shell and tube
with catalyst on shell side
• Due to the second reactor
the BWR can be smaller

Figure C-9: Scheme of two-

reactor Gas-cooled reactor Water-cooled reactor
(second reactor) (first reactor)

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 6. Lurgi MegaMethanol process

High
conversion
efficiency

Minimized
investment
Low recycle
cost for
ratio
large scale Advantages
plants of two-
stage
reactor

Reduced
Low natural
line/
gas
equipment
consumption
sizes

37
 Operating condition

Table C-1. Operating conditions of Lurgi and ICI process

Lurgi process ICI process

Reforming Combined One-step

- Pressure 3.5 MPa 2 MPa

- Temperature 960 °C 880 °C

Reactor Two-stage reactor Single reactor

- Pressure 8 MPa 8-10 MPa

-Temperature 240 °C 240-270 °C

- Catalyst High selective Cu-catalyst

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 D. CONCLUSION

• Syngas is one of the most important chemical in Petrochemical

industry, which can be produce from many kind of materials (NG,
coal, biomass,…) by steam reforming.
• Methanol is produced commonly as an intermediate chemical to
produce many other important chemicals (Formaldehyde, MTO/MTP
processes,…
• Methanol is produced in main types of reactor: Adiabatic reactor and
Isothermal reactor at low pressure and low temperature.
• The process is highly affected by 4 factor: Dimension of reactor,
Temperature, Pressure and CO/H2 ratio.

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THANK
YOU