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Chemistry · Ch 9 — Hydrogen

Commercial Production of Dihydrogen

9.3.2

Commercial Production of Dihydrogen

Industrial Routes

Several large-scale processes supply dihydrogen commercially.

1. Electrolysis of acidified water. Using platinum electrodes, water is split directly:

2H2O(l)→electrolysis, trace acid/base2H2(g)+O2(g)2H_2O(l) \xrightarrow{\text{electrolysis, trace acid/base}} 2H_2(g) + O_2(g)

2. High-purity electrolysis. Electrolysing warm aqueous barium hydroxide between nickel electrodes gives dihydrogen of very high purity (>99.95%).

3. By-product of the chlor-alkali process. When brine (aqueous NaCl) is electrolysed to manufacture NaOH and Cl2Cl_2, hydrogen appears at the cathode as a by-product:

  • Anode: 2Cl−(aq)→Cl2(g)+2e−2Cl^-(aq) \rightarrow Cl_2(g) + 2e^-
  • Cathode: 2H2O(l)+2e−→H2(g)+2OH−(aq)2H_2O(l) + 2e^- \rightarrow H_2(g) + 2OH^-(aq)
  • Overall: 2Na+(aq)+2Cl−(aq)+2H2O(l)→Cl2(g)+H2(g)+2Na+(aq)+2OH−(aq)2Na^+(aq) + 2Cl^-(aq) + 2H_2O(l) \rightarrow Cl_2(g) + H_2(g) + 2Na^+(aq) + 2OH^-(aq)

4. Steam reforming of hydrocarbons or coke. Passing steam over hydrocarbons or coke at high temperature, with a catalyst, produces a mixture of CO and H2H_2:

CnH2n+2+nH2O→Ni, 1270 KnCO+(2n+1)H2C_nH_{2n+2} + nH_2O \xrightarrow{Ni,\ 1270\ K} nCO + (2n+1)H_2

For methane specifically:

CH4(g)+H2O(g)→Ni, 1270 KCO(g)+3H2(g)CH_4(g) + H_2O(g) \xrightarrow{Ni,\ 1270\ K} CO(g) + 3H_2(g)

This CO + H2H_2 mixture is called water gas, or more generally synthesis gas ("syngas"), since it feeds into methanol and hydrocarbon synthesis; syngas can also be made from waste materials such as sewage, sawdust, scrap wood and newspaper. When made from coal, the process is called coal gasification:

C(s)+H2O(g)→1270 KCO(g)+H2(g)C(s) + H_2O(g) \xrightarrow{1270\ K} CO(g) + H_2(g)

Boosting hydrogen yield — the water-gas shift reaction. Reacting the CO from syngas further with steam, using an iron chromate catalyst, converts more CO into extra hydrogen: …