P3

Uses of Hydrogen
Ammonia Synthesis
Methanol Synthesis
Formaldehyde Synthesis
Urea Synthesis

Methanol Synthesis

Methanol Synthesis

Introduction
Uses of methanol
Methanol production via :
1. Partial Oxidation (POX)
2. Steam Reforming

Thermodynamics aspects
Kinetic aspects
Catalysts and process conditions

Introduction

Methanol production takes place via the following reaction:

CO + 2H2
CH3OH or
CO2 + 3H2
CH3OH + H2O
Thus, for methanol production H:C ratio required must be
between 2 to 3.

Methanol process is divided into 3 main sections

i. Production of synthesis gas via
1. Partial oxidation (POX), or
2. Steam reforming, or
3. Coal gasification
ii. Methanol synthesis
iii. Methanol purification

Introduction
i. Syngas from steam reforming
CO + 3H2 (T = 800oC, P = 20atm)
CH4 + H2O
But the ratio has to be adjusted from 1 : 3 to 1 : 2
How:
CO + H2O
CO2 + H2
consume H2
ii. Methanol Synthesis
CH3OH
CO + 2H2
Cat : metal / support ZnOx, CrOx
Exothermic reaction :
T = low (300oC), P = high (350atm) - Dupont
CH3OH + H2O
CO2 + 3H2

Uses of Methanol
1.
2.
3.
4.
5.
6.
7.
8.

Acetic Acid
Chloromethanes
Dimethylterephthalate
Formaldehyde
Methyl metacrylate
MTBE
Gasoline blending
Solvents

Methanol Production via Partial Oxidation

In POX process, O2 content can be adjusted so that H2:CO 2

CH4 + 3/2 O2
CO + 2H2

Use steam converter (shift conversion) to achieve this by removing

excess CO followed by absorption of the CO2 formed.
CO + H2O
CO2 + H2

Basic schemes of POX is similar to hydrogen and ammonia production

Two schemes :
a) Figure (1)
Catalyst cannot tolerate sulfur derivatives. Feedstock must be
desulphurized to sulfur content of 0.05 to 0.1ppm. Part of gas
passes through CO conversion unit then remixed with the
untreated fraction and then partly decarbonated.
b) Figure (2)
Catalyst is resistant to sulfur compounds. Partial CO
conversion is followed by simultaneous desulphurization and
decarbonation.

Methanol Production via Partial Oxidation

Fuel oil/coal

Partial Oxidation

O2

H2S Absorption

Distillation
Steam
Air

N2

Sulfur
Claus

Shift Conversion
CO2 Absoprtion

CO2

CH3OH Synthesis

Steam

Distillation
CH3OH

Base scheme for methanol manufacture using steam reforming Figure (1)

Methanol Production via Partial Oxidation

Fuel oil/coal

Partial Oxidation

O2

Distillation
Shift Conversion
Air

CO2 Absoprtion
N2

Steam

CO2
+ H2S

CH3OH Synthesis
Distillation
CH3OH

Base scheme for methanol manufacture using steam reforming Figure (2)

Methanol Production via Partial Oxidation

Both methods require installation of a sulfur barrier (e.g. zinc oxide) to
protect the synthesis catalyst
Desulphurization has to be completed but decarbonation can be partial
thus it is better to employ solvent that can achieve both objectives
Physical solvents would be able to perform this task (as practiced
by Selexol, Rectisol, etc.)
If operation is at low/moderate pressure, compressor is not necessary
(colored red)

Methanol Production via Steam Reforming

Simpler method because does not require CO conversion, CO2

removal and methanation

An auxiliary compressor is however needed

Methanol production via steam reforming has 2 major sections:

a) Feedstock pretreatment : remove all traces of sulfur
compounds or any other impurities harmful to the synthesis
catalyst (e.g. chlorine)
b) Steam reforming furnace with its auxiliary flue-gas heat
recovery facilities

H2/CO ratio obtained from steam reforming is usually in the

range of 3 to 4 but desired value is between 2 and 3 (shown in
Table on next slides)
Hence the synthesis gas is either too rich in H2 or too poor
in C

Methanol Production via Steam Reforming

Gas / naphtha

Desulphurization

Steam

Steam Reforming

CH3OH Synthesis
Steam
Distillation
CH3OH

Base scheme for methanol manufacture using steam reforming

Methanol Production via Steam Reforming

H2O/CH4 Ratio Scheme for Methanol Manufacture Using Steam Reforming
T (oC)

650

700

800

850

990

1. H2O/CH4 = 1
H2/CO.

4.66

4.00

3.07

3.00

3.00

2. H2O/CH4 = 1.5
H2/CO.

5.75

4.63

3.96

3.70

3.70

3. H2O/CH4 = 2
H2/CO.

3.90

5.00

4.70

4.54

4.48

4. H2O/CH4 = 3.5
H2/CO.

10.25

To obtain desired ratio of H2/C (between 2 to 3) :

1. Purge resulting in a loss of energy related with separation and
compression of excess hydrogen
2. Addition of CO2 upstream or down stream of steam reforming (from
CO2 removal unit or recovered from flue gases of the reforming furnace)

Thermodynamic Aspects
Two main rxns used for CH3OH synthesis
CO + 2H2
CH3OH
Ho298 = -90.8 kJ/mol
CO2 + 3H2
CH3OH + H2O
Ho298 = -49.5 kJ/mol
Exothermic and endentropic reaction

Equilibrium of methanol synthesis from reformed gas produced by steam reforming of methane

Kinetic Aspects
CO + 2H2
CO2 + 3H2
CO + 3H2
2CH3OH

CH3OH
___ (1)
CH3OH + H2O (Residual CO2 + H2)
___ (2) Side
CH4 + H2O (Methanation rxn)
___ (3) reactions
CH3-O-CH3 + H2O (Formation of methyl-ether) ___ (4)

How to suppress side reactions

Rxn 2 Reducing [CO2] content in syngas, [CO] : [CO2]
Rxn 3 Limit reaction temperature, ~400oC
Rxn 4 High reaction pressure
Rxn 4 Increase PH2 in the feed
Rxn 3 More active catalysts Zn-Cr to Cu-based

Catalyst and Process Conditions

No.

Catalyst

Temp, oC

Pressure, atm

Companies

i.

Zn-Cr

300

350

Dupont, Kellog, Lummus,

Montecatini, Badger, BASF, etc.

ii.

Cu-Zn

250

50 100

ICI, Lurgi, Ammonia-Casale,

Topsoe, Mitsubishi.

Two main processes developed from the catalyst mentioned above :

i. The first operates at high pressure between 30 and 35 106 Pa abs.
and 350 to 400oC (as stated in the table). Reactors used with this
operating conditions are
Isothermal (with catalyst tubes)
Adiabatic (with multistage catalyst beds)
ii. A later process operates at low pressure which is 5 to 10 106 Pa
abs. at temperature of 240 to 270oC (as stated in the table. Reactor
used are vertical reactors

Next slide shows methanol manufacturing via the ICI process

Reactor

HP Separator

LP Separator

Light ends
Removal

Light ends compounds

Purification

Purge

Light compounds

Condensates

Heat
transfer
fluid

Crude Methanol
Condensates
Recycle
Make-up
Compressor compressor Synthesis gas
Refined
ICI process Methanol

To water
treatment

Crude
alcohols

Reactor for Ammonia Synthesis

ICI Reactor
Lurgi Reactor

Catalyst and Process Conditions

CO + 2H2
CH3OH
H = -109 kJ/mol
CO + 3H2
CH3OH + H2O H = -58.5 kJ/mol
Features :
Equilibrium limited (conversion ~ 7%)

Methanol Purification
cooled to
Production of
CO, H2

CH3OH

CO, H2

CH3OH
synthesis

Distillation

40oC

Purge
Drum
CH3OH

Separator

N2,
CH4,
H2

Not sure
Development in CH4 Utilisation
1. Conversion of CH4 to syngas
2CH4 + O2
2CO + 4H2
Expensive
Energy intensive
2. CO + 2H2
CH3OH
Expensive
Syngas to methanol

Current and Future Trends

1. To directly convert CH4 to CH3OH, organic chemicals
2. To produce hydrocarbons from syngas
2CH4 + O2
2CO + 4H2 (auto thermal partial oxidation)
Catalyst : Fe or Co based catalyst Fischer-Tropsch Reaction
nCO + 2nH2
(CH2)n + nH2O
nCO + nH2
(CH2)n + nCO2
H
= -192 kJ/mol

Products from F T reaction (% wt)

Products

Fluidized Bed

Fixed Bed

C3 C4

7.7

5.6

Petrol (C5 C11)

72.3

33.4

Middle distillates

3.4

16.6

Paraffins semi solid

middle
hard

3.0
-

10.3
11.8
18.0

Alcohols / Ketone

12.6

4.3

Organic Acid

1.0

traces