Definition of The Project

A Methane to Acetic acid plant is to be set up at Brammanbaria in Bangladesh having a capacity

of 300 ton 99% Acetic Acid per day, corresponding to 109500 ton of 99%Acetic Acid per
year, and an intermediate capacity of 450 ton of 91.5% Methanol per day corresponding to ton
of 16500 tons 91.5% of Methanol per year including all offsites, auxiliaries, utilities and
supporting facilities using Industrial Grade Methane (96.48% CH4) fromTitas Gas Field as
raw material.

Product & Raw material

Specifications
Acetic Acid, CH3COOH:

Acetic acid,systematically named ethanoic acid,is an organic compound.It is a colourless liquid

that when undiluted is also called glacial acetic acid. Acetic acid has a distinctive sour taste and
pungent smell.
Liquid acetic acid is a hydrophilicprotic solvent, similar to ethanol and water. It dissolves not
only polar compounds such as inorganic salts and sugars, but also non-polar compounds such as
oils and elements such as sulfur and iodine. It readily mixes with other polar and non-polar
solvents such as water, chloroform, and hexane. With higher alkanes (starting with octane),
acetic acid is not completely miscible anymore, and its miscibility continues to decline with
longer n-alkanes. This dissolving property and miscibility of acetic acid makes it a widely used
industrial chemical, for example, as a solvent in the production of dimethyl
terephthalate.Although it is classified as a weak acid, concentrated acetic acid is corrosive and
can attack the skin.
Table 1.1:Properties of CH3COOH:
Molecular formula
Molar mass
Appearance
Odor
Density
Melting point
Boiling point
Solubility in water
log P
Acidity (pKa)
Basicity (pKb)
Refractive index (nD)
Viscosity
Dipole moment
Specific
heat capacity (C)

CH3COOH

60.05 gmol1
Colourless liquid
Pungent/Vinegar-like
1.049 g cm3
16 C; 61 F; 289 K
118 C; 244 F; 391 K
Miscible
-0.322
4.76
9.198 (basicity of acetate ion)
1.371
1.22 mPa s
1.74 D
123.1 J K1 mol1

Std molar
entropy (So298)
Std enthalpy of
formation (fHo298)
Std enthalpy of
combustion (cHo298)

158.0 J K1 mol1
-483.88--483.16 kJ mol1
-875.50--874.82 kJ mol1

Methanol, CH3OH:
Methanol, also known as methyl alcohol,wood alcohol, wood naphtha or wood spirits. It is
the simplest alcohol, and is a light, volatile, colorless, flammable liquid with a pleasant smell . It
is highly toxic and unfit for consumption. At room temperature, it is a polar liquid, and is used as
an antifreeze, solvent, fuel, and as a denaturant for ethanol.

Table 1.2: Properties of Methanol

Molecular formula
Molar mass
Appearance
Density
Melting point
Boiling point
log P
Vapor pressure
Acidity (pKa)
Refractive index (nD)
Viscosity
Dipole moment
Flash point
Autoignition
temperature
Explosive limits

CH3OH
32.04 gmol1
Colorless liquid
0.7918 gcm3
0.7925 gcm3 @20C
97.6 C (143.7 F; 175.6 K)
64.7 C (148.5 F; 337.8 K)
-0.69
13.02 kPa (at 20 C)
15.5[3]
1.33141[4]
0.545 mPas (at 25C) [5]
1.69 D
11 to 12 C (52 to 54 F; 284 to 285 K)
385 C (725 F; 658 K)
6%-36%

Availability of Raw Materials:

CH4: Bought from Titas Gas Field, Brammanbaria

H2O (cooling, treated, DM water, etc.): Available in Bangladesh.

Raw material specification

Natural Gas from Titas Gas Fiel

Process Selection
Methane to Methanol conversion process

Catalytic Conversion
Features:

Conversion of methane to methanol with an economic yield of 10%

In most experiments with solid catalysts, selectivities to methanol fell rapidly as methane
conversions exceeded 59%
complete oxidation of methane to carbon dioxide (H = -877 kJ/mol) is highly favored
over partial oxidation of methane to methanol (H = -200 kJ/mol)
A noticeable progress, however, has been made in the field of molecular catalysis by
Periana et al., who demonstrated the selective conversion of methane to methanol at
temperatures around 473 K over platinum bipyrimidine complexes. According to their
experiment, 81% selectivity to methyl bisulfate, a methanol derivative, was reached at
methane conversion of 90% in concentrated sulfuric acid
Although these results are promising, commercial applications are hampered by difficult
separation and recycling of the molecular catalyst.

Thermal Cracking

Methane is converted to methanol by partial oxidation to hydrogen gas and carbon

monoxide (synthesis gas or syngas) at high temperatures normally several hundred
degrees celsius
Syngas is then catalytically converted to methanol over a copper or platinum surface, also
at a couple hundred degrees Celsius
It is only around five or ten percent efficient due to accidental total oxidation to carbon
dioxide and water.

Photo-Catalytic Conversion

Ultraviolet light breaks water into a hydrogen and hydroxyl free radical, which are highly
reactive. When a hydroxyl radical reacts with a methane molecule, a hydrogen is
displaced and methanol is produced.

With the use of tungsten oxide or a similar semiconductor, photons of lower energy than
ultraviolet (down to blue) can be used.
Using Of WO as photo-catalyst visible laser light can be used in room temperature
It is highly energy inefficient (only 2-3% efficiency)
The process is not out in commercial production yet

Biological conversion

Conversion combines both methane and ammonia streams using methane-oxidizing

bacteria and ammonia-oxidizing bacteria, in both wild type and genetically modified
forms
Can convert heterogeneous methane feedstocks, unlike existing commercial process
Does not require a pure source of methane
It does not require expensive chemical catalysts
Cleanup and dehumidification processes not required
Widely applicable to digester gas, landfill gas, peatbogs, marshes, and wastewater
treatment facilities
Conversion process is time consuming

ICI process

Catalyst: Copper-Zinc oxide catalyst

Temperature: 200-30000C
Pressure: 5-10 MPa
Activity of this catalyst is more sensitive to impurities (poisoning)
Reduced manufacturing costs.

Methanol to Acetic acid

Cativa Process

Process developer: BP chemicals

Catalyst: Iridium/iodide catalyst
Improved catalyst stability
Allowing operation at low water concentrations
High reaction rates
Reduced formation of liquid by-products
Improved yield on carbon monoxide
Temperature:
Pressure:

Monsanto process

Process developer: Monsanto

Temperature: 150-2000C
Pressure: 30-60 bar
Catalyst: rhodium/iodide catalyst
Selectivity: 99%
To prevent rhodium loss the reactor composition is maintained within limits on water,
methyl acetate, methyl iodide and rhodium concentrations
High H2O concentrations to prevent catalyst precipitation and maintain high reaction
rates

BASF process

Catalyst: cobalt /iodide catalyst

Temperature: 2500C
Pressure: 680 bar
Selectivity: 90% (based upon methanol)