Technology for hydrogen generation from methanol

Methanol solvent is available cheaper than other organic solvents; it is even produced in abundance than other chemical processing solvents. The demand for hydrogen fuel leads to methanol splitting technologies, as per mole balance equation one molecule of methanol contains four hydrogen atoms. With respect to cost, safety and fuel handling, hydrogen can be generated from methanol is small station to supply it for fuel cell cars and power generator in towns.

An idea of small process plants enhance the network of hydrogen production units of small capacity that utilizing liquid methanol as raw material. However to accomplish it the process equipment should be small enough to produce the required capacity and should be maintenance free and support frequent start-up and shutdown as well.

Some of the established technologies for hydrogen generation from methanol

  • Steam reforming: Thermally autonomous micro-channel reactor
  • Membrane reactor technique (Inorganic and organic membranes dual bed models)
  • Fuel cell technique
  • Partial oxidation

Important catalyst used for reforming of methanol

  • Organo-ruthenium
  • Cu/ZnO/Al2O3
  • CuO/CeO2/Al2O3
  • CuO/ZnO/ZrO2/Al2O3
  • CuZnGaOx

Side products like dimethyl ether formed during the reaction affect the thermodynamic equilibrium of methanol and water composition. By the experimental data 220-250oC is optimal operation temperature for the process at the pressure ranging from 5 to 25 atm. Main compounds that affect the conversion are methane and carbon soot.

Scientific conclusion on rate of reaction of hydrogen generation from methanol:

We need a process technology that has capability of producing higher H2. Based on steam reforming, autothermal and partial oxidation technology main reactions that occur in a reactor are:

  • Dimethyl ether formation/ Dehydration of methanol to Dimethyl ether
  • Steam reforming
  • Waster gas shit reaction
  • Methanol splitting

Kinetics of methanol decomposition is very important to design the reactor to obtain optimum conversion. Based on choice of the catalyst one of the four reactions proceeds further than others. The output of the reactor depends on the selection of catalyst, temperature and pressure of the reaction. The rate constant depends on reactor operating temperature and on activation energy. Dimethyl ether formation and water gas a shift reactions have positive activation energy where as methanol decomposition and steam reforming of methane reactions are have negative values.

The first said two reactions are exothermic and next two are endothermic. The four reactions should be balanced to operate with less energy supply to make the process as green and sustainable technology.

One of the tricks is that to initiate first two reactions to generate heat energy. Then use that energy to start and run next two endothermic reactions in same reactor. This method becomes automatic and demands less energy from external means. The reactor works on combination of autothermal partial oxidation and steam reforming technology. Reactions occurring without requirement of energy supply are always good to prevent greenhouse gas producing fossil fuel consumption. If methanol produced from biogas is used as raw material for this technology that the hydrogen produced is a green fuel.

Watch how the Aspen plus process simulation software, reactor model workout methanol decomposition reaction.

Check the results of hydrogen generation from methanol in RGibbs reactor model. For feed of 0.5 kmol/hr of methanol 1.425 kmol/hr hydrogen is produced at 510K and 2 atm.

FEED PRODUCT
RGIBBS RGIBBS
VAPOR VAPOR
Substream: MIXED
Mole Flow   kmol/hr
METHANOL 0.5 5.71E-04
CO2 0 0.4265996
CO 0 0.0726688
H2 0 1.425137
H2O 0.5 0.0734805
DIMET-01 0 8.02E-05
Total Flow kmol/hr 1 1.998537
Total Flow kg/hr 25.02872 25.02872
Total Flow l/min 338.8457 697.2253
Temperature K 500 510
Pressure   atm 2 2
Vapor Frac 1 1
Liquid Frac 0 0
Solid Frac 0 0
Enthalpy   cal/mol -50838.67 -21542.58
Enthalpy   cal/gm -2031.213 -1720.169
Enthalpy   cal/sec -14121.85 -11959.34
Entropy     cal/mol-K -15.56011 4.85415
Entropy     cal/gm-K -0.6216903 0.3876026
Density     mol/cc 4.92E-05 4.78E-05
Density     gm/cc 1.23E-03 5.98E-04
Average MW 25.02872 12.52352
Liq Vol 60F l/min 0.4865383 1.740365

Sensitivity analysis  performed fixing the reactor pressure, feed rate constant. Reactor temperature is varied from 278K to 700K to the H2 production rate. The analysis indicates the high production occurs in the range of 450 to 500K.

Effect of temperatre on hydrogen generation from methanol, analysis graph