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Hydrogen from Fossil Fuels

Lecture 2 8/28/2006

Hydrogen from Hydrocarbons


Highly Volatile Fuels: Natural Gas, Naphtha Steam Reforming Low Volatile Fuels: Heavy Oil, Coal Partial Oxidation/ Autothermal Reforming

CO, H2, CO2, H2O

Shift Reaction

CO2 Scrub H2

Historical Development
CO/H2 mixtures important since 1900s
Water Gas production from Coke
Useful as Fuel

Synthesis of chemicals Synthesis Gas


Ammonia Methanol Fischer-Tropsch Oxo Processes

Chemistry of SteamReforming and Water Gas Shift Reactions

Reaction Chemistry
Steam Reforming:
CnHm + nH2O nCO + (n+m/2)H2 Endothermic Reaction Catalyst: Nickel Based High Temperature (>850oC), High Pressure (2.5 MPa) Hydrocarbons: Natural Gas (methane), Propane, Butane, Naphtha

Reaction Chemistry
Water Gas Shift (WGS) Reaction: Exothermic, Lower Temperature (<500oC) Reaction CO + H2O CO2 + H2 Catalyst: Iron Oxide, Copper Oxide

Thermodynamics
Reaction Hydrocarbon H0 kJ/mol HC Reforming Methane Propane Butane WGS 206.3 498 650 -41.1 H2 68.6 71.1 72.4 -41.1 3 2.33 2.25 1 H/C

Reaction Equilibrium

P = 4 MPa Steam to Methane Ratio: 2

Steam Reforming and Water Gas Shift Reaction Equilibria


Water Gas Shift Reaction
400oC

1000oC

Steam Reforming Reaction

Side Reactions
Methane Cracking CH4 C + 2H2 ; H0 = 74.9 kJ/mol Boudouard Reaction 2CO C + CO2 ; H0 = -172.4 kJ/mol Formation of carbon deposit catalyst deactivation High temperatures (>820oC) suppress these reactions

Energy for Steam Reforming?


Methane as a fuel CH4 + 2O2 CO2 + 2H2O
H0 = -802.4 kJ/mol Methane reforming
Sum of the burning value of for methane and required heat input exactly equals the burning value of 4 hydrogen molecules obtained Other hydrocarbons?

Technology and Production Process

Process Flow Diagram

Production Process
Purification of Feed Stream
Hydrodesulfurization: conversion of organic sulfur to hydrogen sulfide (Co-Mo, Ni-Mo catalysts) Chloride removal: Absorption of HCl by sodium oxide Sulfur removal: Absorption by ZnO

Production Process
Steam Reforming
High Temperature (>850oC) Nickel-based catalysts Fixed bed catalyst tubes in combustion furnace Steam/methane ratio: 3 - 4 Pressure: 1 - 4 MPa Product gas composition close to equilibrium Conversion >80%

Steam Reformer
Cylindrical tubes packed with catalyst placed in rectangular prism furnace Top fired burners in furnace Downward parallel flow of combustion gases and feed gas Very high temperatures achieved in the combustion furnace Heat transfer by radiation

Production Process
Water Gas Shift Reaction
High Temperature Shift Reaction
Iron oxide-chromia catalyst 300-450oC CO conversion: 90-95%

Low-Temperature Shift Reaction


CuO-ZnO catalyst 200-300oC

Production Process
CO2/H2 Separation
Absorption of CO2
Chemical: Monoethanolamine Physical: Methanol (rectisol), sulfolane (sulfinol), dimethylether of propylene glycol (selexol), etc.

Adsorptive purification
Zeolites (PSA)

Production Process
CO2/H2 Separation
Membrane Separations
CMS (carbon molecular sieves): hydrogen permeation Nanoporous carbon membranes: carbon dioxide permeation

Production Process
Methanator:
Reverse of steam reforming reaction Convert unreacted CO to methane CO a poison for the ammonia synthesis catalyst (Fe/Alumina-zirconia-K2O), methane not a poison

Preferential Oxidation of CO
CO + O2 CO2

Production Process
Preformer
Low temperature (500oC) catalytic reactor upstream of the main reformer Conversion of heavier feedstock (e.g., naphtha) to methane Catalyst: Dispersed NiO on alumina

Steam-Reforming Process
0.66 MJ of hydrogen produced per MJ of fossil fuel consumed Resource consumption: 3.8 tons/ton H2 Major emission: CO2 (~0.5 m3/m3 of H2) Minor emissions: Methane, NOX, SOX, Non-methane Hydrocarbons, CO, etc. Global Warming Potential: 12 ton CO2-equivalent/ton H2
Spath P.L., Mann M.K. 2001, DOE Report, NREL/TP-570-27637

Developments

Developments
Membrane Reactors
Hydrogen removal from the reaction zone to shift the equilibrium of the steam reforming reaction Pd-Ag membrane Operation at less severe conditions Smaller reactors Very low CO contamination in product gas

Developments
Sorption Enhanced Reforming (SER)
Packed bed reactor containing catalyst and an adsorbent for carbon dioxide Steam/methane ratio ~ 6 Temperature: 400-500oC Pressure: 0.1-0.5 MPa Product gas: 90% hydrogen
Major impurity: unconverted methane

Developments - SER
Minimization of side reactions (coking) Cyclic operation
Reaction followed by desorption of carbon dioxide from exhausted adsorbent Adsorbent: K2CO3/Hydrotalcite (synthetic aluminum magnesium hydroxycarbonate) Catalyst?
Hydrogen is required to remove carbon dioxide as methane for nickel catalysts Alternate catalysts?

Developments
Partial oxiation
Mildly exothermic reaction CH4 + O2 CO + 2H2; H0 = -36 kJ/mol H2/CO ratio = 2, excellent for Fischer-Tropsch or Methanol synthesis Pure oxygen required Monolith catalytic (Pt or Rh) reactor Very short residence time (mS) Temperatures ~600oC

Developments Partial Oxidation


Reaction mechanism?
Combustion-Reforming
Oxidation of methane to carbon dioxide Carbon dioxide reforming of methane

Pyrolysis-Oxidation
Dissociation of methane Oxidation of dissociated species

Pathway dependent upon the catalyst Pyrolysis-oxidation dominant at high temperatures (>923K or 650oC)

Developments Partial Oxidation


Efficiency: ~50%, lower than the conventional steam reforming Greater selectivity for synthesis gas Compactness Non-catalytic partial oxidation
Higher Temperatures: 1100-1500oC Useful for higher hydrocarbons as well

Developments Partial Oxidation


Higher Hydrocarbons C6H14 + 3O2 6CO + 7H2
O2/C ratio: 0.5-0.6, less than stoichiometric Thermal Partial Oxidation Units
High Temperature: 1200-1600oC High Pressure: ~7MPa Use of low quality petroleum residue/coal/coke Noncatalytic H2/CO ratio < 2

Developments
Autothermal Refining
Partial oxidation and steam reforming in one reactor
Inlet zone: oxidation by oxygen/enriched air Second zone: steam reforming Net reaction CH4 + xO2 + (1-x)H2O CO + (3-x)H2
Oxygen Needed No external heat required

Developments
Dry Reforming of Methane
Solution for fixing carbon dioxide (?) CH4 + CO2 2CO + 2H2; H0 = 247 kJ/mol H2/CO ratio = 1 T:950oC+ (noncatalytic) Catalytic (NiO-MgO, noble metals): 600700oC Catalyst deactivation due to
Methane cracking CO disproportionation

Developments
Tri-reforming of natural gas Utilization of waste flue gas from fossil-fuel power plants to obtain synthesis gas Reactions CH4 + CO2 2CO + 2H2 CH4 + H2O CO + 3H2 CH4 + O2 CO + 2H2 CH4 + 2O2 2CO2 + 2H2O

Developments Tri-reforming

Developments Tri-reforming

Natural Gas

Syngas H2/CO ~1

Developments Tri-reforming
Advantages
Eliminate carbon dioxide separation Hydrogen/CO ratio ~2 Minimize coke formation Use of waste flue gas Tri-generation No existing industrial process No existing suitable catalyst Heat and Mass Management Inert gas handling

Disadvantages

Thermal Cracking

Thermal Cracking of Methane


Decomposition of hydrocarbons at high temperature CH4 C + 2H2 ; H0 = 74.9 kJ/mol Temperature: 700-980oC Absence of air/oxygen Production of carbon black for rubber tire vulcanization and printing industry Firebrick furnace: methane combustion to obtain high temperatures, followed by decomposition on bricks

Thermal Cracking of Methanol


Catalytic decomposition: CH3OH CO + 2H2 ; H0 = 91 kJ/mol
Impurities: methanol, methane, ether

Steam reforming: CH3OH + H2O CO2 + 3H2 H0 = 50 kJ/mol


Excess of steam prevents the first reaction

Temperature: 250-300oC Pressure: 1-2.5 MPa Catalyst: copper-zinc

Coal Conversion

Steam-Coal Gasification
Process
Two chemical reactions
Pyrolysis: Rapid reaction expelling volatile constituents CHxOy (1-y)C + yCO + 0.5xH2 CHxOy (1-y-x/8)C + yCO + 0.25xH2 + x/8CH4
Gasification of residual carbon: Slow reaction C + H2O CO + H2

T: 600-1000oC, P: 70 bar Endothermic reaction: 163 kJ/mol


C + 2H2O CO2 + 2H2

Decreases with an increase in temperature

CO:H2 ratio ~ 1

Equilibrium Compositions in Coal Gasification

Gasification Reactors

Reactor Comparison

Coal Cracking
HYDROCARB Thermal Cracking of Coal
CH0.8O0.016N0.016 + CaCO3 C + 0.32H2 + 0.08H2O + 0.008N2 + 0.016CaS
C: Carbon Black as clean fuel Hydrogen: Byproduct Fuel

Carbon Dioxide-free fossil fuel based hydrogen

Hydrogen from Coke Formation


Coke furnace gas was a major source of hydrogen until coal gasification Reactions similar to thermal cracking shown earlier
CH0.8O0.2 0.8C + 0.4H2 + 0.2CO

Steam-Iron Process
Reduction of Iron Oxides
Fe3O4 + H2 3FeO + H2O Fe3O4 + CO 3FeO + CO2 FeO + H2 Fe + H2O FeO + CO Fe + CO2

Oxidation of Iron
Fe + H2O FeO + H2 3FeO + H2O Fe3O4 + H2

Process cyclic with respect to iron-iron oxides

Coal Gasification Research and Developments


Advanced reactor configurations: circulating fluidized bed reactor Use of pure oxygen/oxygen enriched air: membrane separations for oxygen Membrane separations for product gas In-Situ coal gasification

Coal Gasification Research and Developments


CO2 separation and capture during reaction (e.g., capture using CaO) Resource recovery from byproducts (sulfur to sulfuric acid, slag for road construction) Mixed feedstock (biomass, municipal waste)

Conversion of Oil

Partial Oxidation of Oil


Hydrogen from heavy oil (remainder of crude oil distillation) Noncatalytic process
Temperature : 1150-1315oC Pressure: 1-10 MPa

Reactions
CnHm + nH2O nCO + (n+m/2)H2 CnHm + n/2 O2 nCO + m/2 H2
Water gas shift reaction

Partial Oxidation of Oil


Heavy Oil:
Residual Oil: n = 1 m = 1.3 CO/hydrogen ratio ~1

Lighter Hydrocarbons
Catalytic Process Lower Temperature

Hydrocracking
Conversion of heavy oil into lighter oil and gasoline fractions Require input of hydrogen and heat High Pressure: 10 MPa Temperature: 320-400oC Catalytic process Net hydrogen yield: 3.7 Nm3/kg heavy oil

Fossil fuel-based hydrogen should not have any greenhouse gas emissions associated with it for enjoying the full environmental benefits of the hydrogen economy.

Appendix
Reaction Mechanisms

Mechanism of Steam Reforming Reaction


Dissociative Adsorption of Steam and Methane H2O(g) H2O (s) H2O (s) O(s) + H2(g) CH4(g) CH2(s) + 2H(s) Reaction Between Adsorbed Species CH2(s) + O(s) CHO(s) + H(s) CHO(s) CO(s) + H(s) CO(s) + O(s) CO2(s) CHO(s) + O(s) CO2(s) + H(s)

Mechanism of Steam Reforming Reaction


Desorption of Products CO2(s) CO2(g) 2H(s) H2(g) CO(s) CO(g)

Mechanism of WGS Reaction


Adsorptive (Formate) Mechanism H2O(g) H2O (s) CO(g) CO(s) H2O(s) + CO(s) Intermediate(s) Intermediate(s) CO2(s) + H2(s) CO2(s) CO2(g) H2(s) H2(g)

Mechanism of WGS Reaction


Regenerative Mechanism H2O(g) H2O (s) H2O (s) OH(s) + H(s) OH(s) O(s) + H(s) 2H(s) H2(g) CO(g) CO(s) CO(s) + O(s) CO2(s) CO2(s) CO2(g)

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