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Hydrogen production from methanol

1. Introduction
There is a growing necessity to find alternative ways
to produce energy with lower emissions of pollutants
and higher efficiencies compared to internal
combustion. One such option is the use of proton
exchange membrane
(PEM) fuel cell system. PEM fuel cells convert
hydrogen gas into useful electric power with an effi-
ciency that is not limited by thermodynamics and the
only by product is water. Due to current
infrastructure, storage technology and safety
concerns, hydrogen gas cannot be stored on-board in
adequate amounts for mobile applications. On
demand reforming of liquid hydrocarbons to produce
hydrogen is seen as an attractive means of providing
the necessary hydrogen to the fuel cell. With the
exception of formic acid,
Methanol is the easiest hydrocarbon to reform. On
board methanol reforming has a couple of
advantages over other potential fuels: unlike
gasoline or diesel fuel,
Liquid methanol can be easily readily produced by biomass, it is
easy to transport and store. It has high hydrogen density.the basic
way hydrogen generation from methanol is decomposition of pure
metnanol.

It is endothermic reaction with 90.7 kj/mol heat of reaction.


It produces carbon mono oxide which is harmful for health and
poison for fuel cell. So some downstream plants eliminate it before
releasing product gas for fuel gas.
It can also produce come bi-product like di-methyl ether and
methane.
TECHNOLOGY: A mixture of water and methanol with a molar
concentration ratio (water: methanol) of 1.3 - 1.5 is pressurized to
approximately 20 bar, vaporized and heated to a temperature of
250 - 280 °C. The hydrogen that is created is separated through the
use of a hydrogen-permeable membrane made of a palladium and
silver alloy.

There are two basic methods of conducting this process.

• The water-methanol mixture is introduced into a tube-shaped


reactor where it makes contact with the catalyst. The
hydrogen is then separated from the other reactants and
products in a later chamber. The reformed material passes the
PdAg membrane and most of the hydrogen passes through.
• The other variety features an integrated reaction chamber and
separation membrane. In such a design the walls of the
reaction chamber are made from a PdAg-coated ceramic
cylinder and the hydrogen is thereby separated directly out of
the reaction chamber.

With either design, not all of the hydrogen is removed from the
product of the reaction, so the remaining gas mixture still contains
a significant amount of hydrogen. As such, this resulting mixture is
often mixed with air and burned. The heat energy produced by
burning this mixture can be used for heating purposes.

Advantages and disadvantages

Methanol reformers are being considered as a component of a


hydrogen fuel cell-powered vehicle. A prototype car, the NECAR
5, was introduced by Daimler-Chrysler in the year 2000. The
primary advantage of a vehicle with a reformer is that it does not
need a pressurized gas tank to store hydrogen fuel; instead
methanol is stored as a liquid. The logistic implications of this are
great; pressurized hydrogen is difficult to store and produce. Also,
this could help ease the public's concern over the danger of
hydrogen and thereby make fuel cell powered vehicles more
attractive. However, methanol, like gasoline, is toxic and (of
course) flammable. The cost of the PdAg membrane and its
susceptibility to damage by temperature changes provide obstacles
to adoption.

Another problem is that although hydrogen power produces energy


without CO2, a methanol reformer creates the gas as a byproduct.
The high level of greenhouse gases in our atmosphere significantly
contributes to global warming.

Methanol (prepared from natural gas) that is used in an efficient


fuel cell, however, releases less CO2 in the atmosphere than
gasoline, in a net analysis.

EFFECT OF CATLYTIC FORMATION AND


REACTION CONDITION ON PRODUCTION OF
HYDROGEN FROM METHANOL THROUGH
DECOMPOSITON OVER Pt AND Pd CATALYSTS –
CATALYST PREPARATION-
Steps to prepare Pt/Al2O3 and Pd/Al2O3-
1).Method, a known amount of aluminum
isopropoxide (AIP), 98% was hydrolyzed in water at
85 deg C.
2). Then a small amount of nitric acid was added to
obtain a clear sol.
3). After that, the necessary amount of either
H2PtCl6 or Pd(NO3)2 precursor was added to obtain
the desired metal loading (from 1 to 10 wt %) in the
final catalyst formulation.
4). Pt or Pd precursor solution was added last.
5). After evaporating the excess solvent. Gel form is
obtained and then dried at 110 _C for 24 h to remove
water and solvent.
Effects of Pt loading-effect of Pt loading on
decomposition of metnanol and composition of
product steam.
1).three loading of Pt were investigated-2%, 5%, 9%

The results of the activity tests for different Pt


loading catalysts on sol–gel alumina are displayed in
Fig.
2). Decomposition activity was increased when the
Pt loading was increased from 2% to 9%. The
complete conversion temperature dropped from 405
to 390 deg C. Further increasing the loading had no
effect on the activity.

3). The 5% and 9% Pt catalysts exhibited essentially


100% hydrogen selectivity for all conversions
(hydrogen selectivity is defined as the fraction of
hydrogen in methanol that ends up as molecular
hydrogen).
4). The 2% Pt catalyst started forming methane at
360 deg C and the selectivity for hydrogen dropped
to 92% at the maximum conversion temperature of
405 deg C.

5). Since production of maximum amount of


hydrogen is the goal, the methanation reaction is

From the methanation (2) reaction, H2O is formed.


Water can participate in the water gas shift reaction
(WGS)

6). The production rates of hydrogen are 289 mmol/s


kg for the 9% Pt catalyst, for the 2% Pt it is 273
mmol/s kg catalyst because of the lower selectivity.
Hydrogen Production of Methanol Reformation Using
Cu/ZnO/Al2O3 Catalyst:

The catalytic performance of methanol reformation using


Cu/ZnO/Al2O3 was investigated at low temperature. The
operation conditions, such as composition of Cu, Zn, and Al,
temperature, molar ratio of H2O/CH3OH, weight hourly space
velocity, catalyst weight, and kind and flow rate of carrier gas
(helium and air), were evaluated to obtain the optimum
reaction condition. The catalysts were prepared by oxalic
coprecipitation, coprecipitation, and polyol method. The
weight composition of Cu, Zn, and Al prepared by oxalic
coprecipitation was 15:15:5 by high-throughput screening of
combinatorial chemistry method, which was the best
Cu/ZnO/Al2O3 catalyst. The prepared catalysts showed high
activity and selectivity towards hydrogen formation. The
methanol conversion, production rate, and volumetric
percentage of hydrogen using this best catalyst were larger
than 95%, 0.65 mol/h·g and 59%, respectively, and the CO
volumetric percentage was smaller than 0.22% when the
reaction temperature was 240 °C.

PRASHANT MISHRA
B.TECH.(AUTOMOTIVE DESIGN ENGG.)
UNIVERSITY OF PETROLEUM AND
ENERGY STUDIES
DEHRADUN (U.K.)