Liquid-Liquid Extraction Lecture 23 26 Nov 2012 1 Overview •Liquid-Liquid Extraction •(solvent extraction) •Pioneered during 1940’s (uranium purification) •Alternative to distillation, absorption/stripping •Energy savings •Sometimes easier separation •Lower temperatures •Usually two distinct phases formed •Usual purpose, to either purify the •Raffinate, or •Solute 2 Liquid-Liquid Extraction Extract Feed [a+b] [s + a] (+b) Extractor Solvent [s] a = solute b = diluent s = solvent Raffinate [b] (+ a & s) let: x mass fraction solute in raffinate y mass fraction • Separation accomplished by chemical differences • Usually in two phase • - light phase • - heavy phase • Usually coupled with another separation technique Separator could be: column w/ stages or packing column with moving internals single stage mixer/settler equilibrium stage(s) phase solute in extract phase y * in equilibriu m with associated x 3 Example Industrial Processes Seader & Henley (2006) 4 Typical LL Extraction Process Seader & Henley (2006) 5 Equipment Examples Treybal (1980) Seader & Henley (2006) 6 7 8 9 Spray Columns: Seader & Henley (2006) 10 Packed-bed Column Seader & Henley (2006) Light liquid - dispersed phase Treybal (1980) 11 Sieve-tray Extraction Column: light phase dispersed Treybal (1980) 12 Oldshue-Rushton (Mixco Lightnin CMContactor) column Scheibel column Seader & Henley (2006) 13 Seader & Henley (2006) 14 Podbielniak Extractor Treybal (1980) 15 Equipment Seader & Henley (2006) 16 Equipment Examples Seader & Henley (2006) 17 Equilateral Triangular Diagrams [a] R [ kg ] raffinate E [ kg ] extract mixture mixture M [ kg ] combined mixture Overall material balance: RE M [b] [s] Rearrange: [kg ] Component material balance (on a): xR R yE E xM M R E yE xM xM xR Lever principle: R E [s] e m EM MR [b] 18 Equilateral Triangular Diagrams [a] [a] [b] [s] [b] [s] Type I Type II Examples: Example: • water (b), ethylene glycol (a), furfural (s) • water (b), acetone (a), chloroform (s) • n-heptane (b), methylcyclohexane (a), aniline (s) 19 Distribution Curves [a] yE [b] [s] xR Type I [a] [b] [s] Type II 20 Distribution Curves [a] yE [b] [s] xR Type I [a] yE [b] [s] Type II xR 21 Distribution Curves [a] yE [b] [s] xR Type I [a] yE [b] [s] Type II xR 22 Effect of Temperature (and Pressure) Treybal (1980) 23 Effect of Temperature (and Pressure) Treybal (1980) 24 Choice of Solvent •Selectivity separation factor ya y b extract 1; better 1 xa x b raffinate •Distribution Coefficient better if K 1 •Insolubility of Solvent better if less soluble in R phase •Solvent Recoverability should be easy to separate solvent from E and R •Density large density differences between the two phases is desired •Interfacial Tension would like large for easier coalescence of dispersed phase •Others: • solvent stable, inert, nontoxic, nonflammable, low cost • low viscosity • low vapor pressure • low freezing point 25 Mixer – Settler (single stage extraction) Raffinate Feed New Solvent Solvent settler mixer Extract solvent recovery solvent recovery Purified Raffinate Purified Extract Recycled Solvent F Black Box: S Raffinate Feed xF Solvent yS 1 stage xR Extract yE R [a] E Material balance: F S RE M [s] [b] 26 Mixer – Settler (single stage extraction) given: xF , F , yS , S find: xM , M , xR , yE , E , R Component material balance (on a in feeds): x F F y S S x M M xM xF F yS S F S Component material balance (on a in products): x R R y E E x M M E M xM xR [a] yE xR [s] [b] 27 Mixer – Settler (single stage extraction) Minimum Solvent (rate): S min F FD DS xF xD Maximum Solvent (rate): S max F FK KS [a] xD yS [s] [b] xF xK xK yS 28 Cross-Current (multi-stage extraction) E1 F Stage 1 Feed xF E2 y1 R1 Stage 2 x1 E3 y2 R2 x2 Final Extract y3 Stage 3 Solvent S Solvent S Solvent S yS yS yS R3 x3 Final Raffinate [a] Final Extract: y FE E1 E 2 E 3 y1 E 1 y 2 E 2 y 3 E 3 E1 E 2 E 3 [s] [b] 29 Continuous Multistage Countercurrent Extraction Feed F xF Extract E1 y1 Total MB: 1 R1 x1 R2 2 x2 E3 y3 E2 y2 RN 2 xN 2 E N 1 y N 1 N-1 R N 1 x N 1 N EN yN RN xN Raffinate S yS Solvent F S E1 R N M Total MB on a: x M xF F yS S [a] F S If y1 & x N known (specified), then flowrates E 1 & R N can be found. [s] [b] 30 Continuous Multistage Countercurrent Extraction Feed F xF Extract E1 y1 1 R1 x1 R2 2 x2 E3 y3 E2 y2 Total MB: R N S F E1 Operating Point: R F E 1 RN 2 xN 2 E N 1 y N 1 N-1 R N 1 x N 1 N EN yN RN xN Raffinate S yS Solvent MB from feed to N-1 stage: R N 1 E N F E1 [a] R [s] [b] 31 Continuous Multistage Countercurrent Extraction Feed F xF Extract E1 y1 1 R1 x1 R2 2 x2 E3 y3 E2 y2 RN 2 xN 2 E N 1 y N 1 N-1 R N 1 x N 1 N EN yN RN xN Raffinate S yS Solvent Now step off to find number of equilibrium stages: [a] R [s] [b] 32 Questions? 33