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Content archived on 2024-04-15

DEVELOPMENT OF GASEOUS PERMEATION MEMBRANES ADAPTED FOR THE PURIFICATION OF HYDROCARBONS

Objective


The manufacturing process for hollow fibres for hydrocarbon purification was investigated. Relationships between manufacturing parameters, membrane permeability and selectivity, and membrane structure were extensively studied.

In parallel, chemical engineering and economic evaluation studies were carried and led to the definition of 2 target membranes well adapted to natural gas dehydration: M1 (G/methane) = 5E-5cm{3} STP/cm{2}5cm Hg, water/methane = 300) which can be used without sweeping gas on the low pressure side, and membrane M2 (G/methane) = 5E-6cm{3} STP/cm{2}5cm Hg, water/methane = 500) which needs a sweeping gas.

The manufacture of hollow fibres and modules was optimised. Several tens of minimodules containing 30 to 200 fibres (each 30 cm long) were tested on synthetic gas mixtures. 3 of these were tested during a 4 month period on a commercial terminal of natural gas dehydration.

Various polymers, in the form of dense films and flat asymmetric membranes were assessed in order to select the basic polymer for membrane manufacture. The main criteria were intrinsic permeabilities and selectivities, chemical and mechanical stability and processability for membrane manufacture using a dry-wet spinning process.

The following characteristics were defined for the membranes to be developed: carbon dioxide/methane selectivity of more than 50; hydrogen sulphide/methane selectivity of more than 50; water/methane selectivity of more than 200; permeability to methane comprised between 1E-4 and 1E-6 cm{3} STP/cm{2} s cm Hg.

A specific polyimide proved to present adequate characteristics to elaborate the membranes of the objective, especially for the dehydration of natural gas (water/methane and carbon dioxide/methane intrinsic selectivity of 236 000 and 76 respectively).

Due to a very limited choice of solvents for this polymer it was possible, using a dry-wet spinning process, to manufacture raw hollow fibres presenting a skin simultaneously thin enough and free of defects.

By combining 2 finishing treatments - high temperature stretching and an impregnation with a hydrophillic agent - hollow fibres were produced which have the appropriate mechanical strength and water/methane selectivity for natural gas dehydration. Nevertheless, the effective permeability to water vapour of these fibres is still too low to consider their use in industrial applications to be economically attractive.
THE OBJECTIVE OF THE PROJECT IS TO STUDY AND DEVELOP GASEOUS PERMEATION MEMBRANES ADAPTED TO THE TREATMENT OF A RAW NATURAL GAS TO MEET PIPELINE SPECIFICATIONS FOR TRANSPORTATION.
NATURAL GAS DEHYDRATION AND PARTIAL ACID GASES REMOVAL ARE NECESSARY. NEW MEMBRANES PRESENTING A HIGH STABILITY IN PRESENCE OF A RAW GAS AS WELL AS SEPARATION PROPERTIES ADAPTED TO THE PROBLEM OF GAS DEHYDRATION ARE RESEARCHED.

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Coordinator

GROUPEMENT EUROPÉEN DE RECHERCHES TECHNOLOGIQUES SUR LES HYDROCARBURES
EU contribution
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Address
Avenue Napoléon Bonaparte 232
92500 RUEIL MALMAISON
France

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