Part III.

CHEMICAL REACTION and BIOTECHNOLOGY

Lesson 7 Unit Operations involving Chemical Reaction

Alberto Coz
Department of Chemistry and Process & Resource Engineering University of Cantabria coza@unican.es

INDEX
1.- Basic principles 2.- Reactive Distillation 3.- Reactive Absorption/Adsorption 4.- Reactive Extraction 5.- Membrane Reactors Examples

1.- Basic principles

They comprise the unit operation of mass transfer with simultaneous chemical reactions within a single apparatus.
An increase in research and innovation. - Mass balances - Thermodynamic concepts - Chemical equilibrium - Kinetics
CA
liquid interface

CR Ceq

Cs,eq

2.- Reactive Distillation

Rectifying section

Stripping section

Industrial applications: Etherification: MTBE, ETBE, TAME. Esterification: Methyl Acetate and other esters. Polymers: dimerisation, oligomerisation. Hydrolysis. Hydrogenation, hydrocracking.
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3.- Reactive Absorption

Industrial applications: - Gas industry: Gas dehydration, Removal of CO2 and H2S. - Refineries: Hydrocarbon absorbers for lean oil etc., H2S absorbers. - Petrochemical industry: Synthesis gas processing, Ethylene oxide absorption. - Chemical industry: Synthesis gas processing (CO2 removal), HCl and ammonia absorption, Absorption of nitrous gases. - Cellulose industry: Sulphur dioxide absorption, Chlorine dioxide absorption, Flue gas desulfurisation. - Food processing: Stripping various components producing odours, Processing fatty acids. - The metal and packaging industries: Absorption of triethylamine (in foundries), Absorption and recovery of solvent vapours. - Wastewater/sewage treatment and pollution control: removal of chlorinated hydrocarbons, Desorption and recovery of ammonia, Effluent neutralization.

3.- Reactive Absorption

Traditional Novel methods:

3.- Reactive Absorption

Modelling:

Usually dominated by the mass transport kinetics

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3.- Reactive Adsorption

Chemisorption: Reaction between the surface and the adsorbate. New bonds: from Van der Waals interactions to covalent bonds

Modelling: - Mass transfer: adsorption. - Reaction terms: kinetics, equilibrium.

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3.- Reactive Adsorption

Applications:

LIQUIDS: - Pharmaceutical: penicillin or antibiotics in reactive adsorbents. - Dyes: wastewater in textile industry. - Environmental applications: phenolic compounds, heavy metals. GASES: - Desulfurisation. - Ammonia, NOx

4.- Reactive Extraction

Reactive extraction is a separation process using the reactions between extractants and the materials extracted. Usually, the extractant in the organic phase reacts with the material in the aqueous phase and the reaction complexes formed are then solubilised in the organic phase. Applications: - Leaching with chemical reactions (phases, especiation: geochemical equilibrium). - Extraction of carboxylic acids. - Pharmaceutical products. - Furfural and others in biorefinery applications (Lesson 8). - Hydrometallurgy: mining metals. Modelling: - Extraction coefficients. - Kinetics and equilibrium.

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5.- Membrane Reactors

A membrane reactor is a bifunctional apparatus combining a membranebased separation with a (catalytic) chemical reaction in one device. 1.- Increase the conversion and selectivity.

Two types:
Extractor type (conversion enhancement) Distributor/contactor type (selectivity enhancement)

Dehydrogenation Esterification Steam reforming Water splitting

Hydrocarbon oxidation Partial hydrogenation Methane to synthesis gas

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5.- Membrane Reactors

2.- Separation of products.

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