This document discusses different types of difficult separations including azeotropes and close boiling mixtures. It describes various means of improving separations such as selectively modifying relative volatility, changing pressure, or adding a mass separating agent. Mass separating agents include non-volatile solvents for extractive distillation and volatile entrainers for azeotropic distillation. Several examples of using azeotropic distillation with different entrainers to separate various mixtures are provided.
This document discusses different types of difficult separations including azeotropes and close boiling mixtures. It describes various means of improving separations such as selectively modifying relative volatility, changing pressure, or adding a mass separating agent. Mass separating agents include non-volatile solvents for extractive distillation and volatile entrainers for azeotropic distillation. Several examples of using azeotropic distillation with different entrainers to separate various mixtures are provided.
This document discusses different types of difficult separations including azeotropes and close boiling mixtures. It describes various means of improving separations such as selectively modifying relative volatility, changing pressure, or adding a mass separating agent. Mass separating agents include non-volatile solvents for extractive distillation and volatile entrainers for azeotropic distillation. Several examples of using azeotropic distillation with different entrainers to separate various mixtures are provided.
This document discusses different types of difficult separations including azeotropes and close boiling mixtures. It describes various means of improving separations such as selectively modifying relative volatility, changing pressure, or adding a mass separating agent. Mass separating agents include non-volatile solvents for extractive distillation and volatile entrainers for azeotropic distillation. Several examples of using azeotropic distillation with different entrainers to separate various mixtures are provided.
Separations 5 Lecture 6 – Separation of azeotropic and close boiling mixtures
John Christy Types of difficult separation • Azeotropes – vapour and liquid have same composition so impossible to separate past azeotrope in single column • Close boiling mixtures – relative volatility less than 1.1 leads to large number of stages and high reflux ratio • Mixtures with volatilities the wrong way round, i.e. nearly all material must go overhead, leading to high cost Means of improving separation • Selectively modify relative volatility of mixture so as to break azeotrope or increase relative volatility of close-boilers. • Achieve by: – Changing pressure (often not practical) – Adding mass separating agent (MSA) • Use a ‘non-volatile’ solvent – Extractive Distillation • Use an entrainer – the volatile entrainer usually is chosen to form a heterogeneous ternary azeotrope – Azeotropic Distillation • For heterogeneous azeotrope, decant liquid Changing pressure
• Azeotrope composition may change with pressure
Changing pressure
• Use higher P for initial separation, then use
azeotrope as feed to low pressure column Changing pressure
• By returning azeotropes into column operating at
different pressure, separation is possible Changing pressure
• If azeotrope composition varies only slightly with
pressure, then recycle flows are very large and overhead flows are massive • NB Azeotrope may disappear at high or low enough P Heterogeneous Azeotropes
• If two liquid phases form, a decanter can be used to
separate D from C when azeotrope E is condensed Heterogeneous Azeotropes
x1 < ya < x2
• If z < x1, then obtain almost pure ‘lvc’ in bottoms
and heterogeneous azeotrope at top Heterogeneous Azeotropes
x1 < ya < x2
• If z > x2, then obtain almost pure ‘mvc’ in bottoms
and heterogeneous azeotrope at top Heterogeneous Azeotropes
• Pressure alters difference in composition of two liquid
phases Heterogeneous non-Azeotrope
y P2
P1
e.g. mek/water
xL1 xz1 xL2 x
• Column 1 produces azeotrope distillate xz1 at P1 and x=0 bottoms • Flash to P2 and decant xL2 to pump as feed to second column at P1 whose distillate is xz1 and bottoms has x=1 Use of Mass Separating Agents • Can be used for close boiling mixtures, homogeneous azeotropes and in order to reverse volatilities • If a relatively volatile MSA is used, it will be chosen so that it forms an azeotrope (usually min boiling) with either or both of the original components (Azeotropic Distillation) • If a non-volatile solvent is used, it will be chosen to dissolve one component preferentially, allowing other component to leave in distillate (Extractive Distillation Azeotropic distillation • Add substance that forms minimum boiling azeotrope with one or both components. • Take azeotrope off top and separate by decanting or by solvent extraction • May get binary or ternary azeotrope, either homogeneous or heterogeneous Azeotropic distillation - examples • Azeotropes – Benzene/cyclohexane (74°C) use acetone to form azeotrope with cyclohexane (53.1°C) and water wash to recover acetone – Ethanol/water – add benzene to form heterogeneous ternary azeotrope (decant) • Close Boilers – Toluene/methylcyclohexane – add methanol to form azeotrope with mch. Gives methanol/toluene in bottoms (water wash) – Butene/butadiene – add ammonia at 16bar – butenes form heterogeneous azeotropes with ammonia Azeotropic distillation - examples • Reverse volatilities – Paraffins/aromatics • add methanol to take paraffins overhead. Water wash then distill • Add nitromethane to take paraffins overhead. Cool and decant Azeotropic distillation - examples
• Form heterogeneous ternary azeotrope with
benzene to separate ethanol/water Azeotropic distillation - examples
• Form heterogeneous binary azeotrope of butene
with ammonia to separate butene/butadiene Azeotropic distillation - examples
• Form binary azeotrope of one component with
acetone to separate benzene/cyclohexane, then use water to extract acetone from cyclohexane
