The separation of hydrogen and carbon monoxide using polymer membranes

  • Anthony B. Hinchcliffe

Student thesis: Doctoral ThesisDoctor of Philosophy


This work studies the development of polymer membranes for the separation of hydrogen and carbon monoxide from a syngas produced by the partial oxidation of natural gas. The CO product is then used for the large scale manufacture of acetic acid by reaction with methanol.
A method of economic evaluation has been developed for the process as a whole and a comparison is made between separation of the H2/CO mixture by a membrane system and the conventional method of cryogenic distillation.
Costs are based on bids obtained from suppliers for several different specifications for the purity of the CO fed to the acetic acid reactor. When the purity of the CO is set at that obtained by cryogenic distillation it is shown that the membrane separator offers only a marginal cost advantage.
Cost parameters for the membrane separation systems have been defined in terms of effective selectivity and cost permeability. These new parameters, obtained from an analysis of the bids, are then used in a procedure which defines the optimum degree of separation and recovery of carbon monoxide for a minimum cost of manufacture of acetic acid. It is shown that a significant cost reduction is achieved with a membrane separator at the optimum process conditions. A method of "targeting" the properties of new membranes has been developed. This involves defining the properties for new (hypothetical -yet to be developed) membranes such that their use for the hydrogen/carbon monoxide separation will produce a reduced cost of acetic acid manufacture.
The use of the targeting method is illustrated in the development of new membranes for the separation of hydrogen and carbon monoxide.
The selection of polymeric materials for new membranes is based on molecular design methods which predict the polymer properties from the molecular groups making up the polymer molecule. Two approaches have been used. One method develops the analogy between gas solubility in liquids and that in polymers. The UNIFAC group contribution method is then used to predict gas solubility in liquids. In the second method the polymer Permachor number, developed by Salame, has been correlated with hydrogen and carbon monoxide permeabilities. These correlations are used to predict the permeabilities of gases through polymers.
Materials have been tested for hydrogen and carbon monoxide permeabilities and improvements in expected economic performance have been achieved.
Date of Award1991
Original languageEnglish
SupervisorBrian Tighe (Supervisor)


  • separation
  • hydrogen
  • carbon monoxide
  • polymer membranes
  • gas separation
  • economic evaluation
  • polymer membrane

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