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Basic principles
In liquid-liquid extraction, a soluble component (the solute) moves from one liquid phase to another. The two liquid phases must be either immiscible, or partially miscible. usually isothermal and isobaric can be done at low temperature (good for thermally fragile solutes, such as large organic molecules or biomolecules) can be very difficult to achieve good contact between poorly miscible liquids (low stage efficiency) extracting solvent is usually recycled, often by distillation (expensive and energy-intensive)
Extraction equipment
Batch: Continuous: single-stage: column:
separatory funnel
Design
Mixer-settlers, both as stand-alone and as incolumn type, are offered for special applications. As implied by the name, the mixer-settler-column is a series of mixersettlers in the form of a column. It consists of a number of stages installed one on top of the Mixer-settlers operate with a purely stageother, eachis hydraulically separated, and each wise contact. After every mixer there a with a mixing ettler. Mixer-settlers can be operated inand a settling zone (see below). This design enables the elimination of some of multistage, co- or countercurrent fashion. the main disadvantages of conventional mixersettlers, whilst maintaining stage-wise phase contact. The mechanical design of the mixer-settlercolumn is comparable to the agitated ECR Khni column. Key characteristics For long residence times: >15 min Extraction controlled by residence time Reactive extraction systems Long phase separation For extraction controlled by pH (stage-wise pH adjustment)
Mixer-settler column
points
Separation of high-boiling products or pollutants that are present in only low concentrations Separation of components with similar boiling points or components forming ction with high mass transfer and/or azeotropes ng physical properties, this is the Separation of mixtures with of choice. The geometry of the thermally sensitive components d compartments can be adapted for Selective separation of single ng hydrodynamic conditions. Other components out of a complex mixture atures are the special mixing turbines Our portfolio includes a complete range of perforated partition plates. liquid-liquid-extraction equipment, enabling us to provide you with the most appropriate solution for your requirements. In addition to agitated columns, it includes mixer-settlers and packed columns. Design The agitated Khni column has a simple and robust design. The drive unit and the shaft are supported at the top of the column, allowing you to use all common types of shaft seals (stuffing box, mechanical seals). In special cases, the seal can be replaced by a magnetic drive. Only radial slide-bearings are necessary
Agitated column
The ECP packed column is based on c Packing The special Sulzer extraction packing Liquid distributors In order to create an even liquid flow Main benefits High specific throughput fac Small column diameters Revamp of existing columns Use in cases of difficult phy Low density difference < 50 Low interfacial tension: < 2 Tendency to form emulsion Reliable scale-up
Stream labeling
feed solvent mixer mixture settler raffinate extract E, yA,1 1 F, xA,0
SE solvent flow rate Solvent (S) extracts A (yA), creating the product = FS = constant
extract stream (E). The depleted feed becomes the product raffinate stream (R).
Equilibrium (no longer VLE!) is defined by the distribution ratio, Kd:
S, yA,N+1 N R, xA,N
Kd = yA/xA Note that yA does not refer to gas composition. Usually specified: yA,N+1, xA,0, FD/FS and xA,N.
(analogous to operating line for stripper column). (FD/FS)max gives FS,min for N = .
1
2 3
X0
(X0,Y1)
R R y = x + (y1 - x0 ) E E Can also use Kremser eqns, if solutions are dilute and equil. line is straight.
mE y N +1 - y 0 mE ln 1 + R y y R 1 0 N= ln R mE
N=3 (XN,YN+1)
Cross-flow cascade
From mass balance around stage j:
R R y j = - xi + (y j ,in + x j -1) Ej Ej
N=3
Increase overall efficiency by introducing fresh extracting solvent at each stage. Each stage has its own mass balance and operating line
(x2,y2) (x3,y3)
(x1,y1)
Uses much more solvent than countercurrent cascade (requires much more solvent recovery)
A mixer-settler is just one cross-flow stage.
x3
(x2,y3,in)(x1,y2,in)
(x0,y1,in)
E
N
Operating lines intersect at feed composition (not shown, may be very large).
3 5 yA,1 1 6
N = 4, F feed stage
Equilibrium data is different for each solute (use separate McCabe-Thiele diagrams!)
If yA,1 and xA,N are specified, and NF is known, use M-T diagram to obtain N, then use trial-and-error to find xB,0 and xB,N+1
xA,N If yA,1 and xB,N are specified, vary NF (trial-and-error) until N is the same for both solutes.
Center-cut extraction
When there are 3 solutes: A, B and C, and B is desired (A and C may be > 1 component each) Requires two columns: column 1 separates A from B+C column 2 separates B from C Requires three extracting solvents: A prefers solvent 1 over solvent 2 B, C prefer solvent 2 over solvent 1 B prefers solvent 3 over solvent 2 C prefers solvent 2 over solvent 3 solvent 1 +A solvent 2
solvent 3 +B
solvent 2
F zA, zB, zC
solvent 1
solvent 2 +B+C
solvent 3
solvent 2 +C
Figure 13-14 Effect of temperature on equilibrium of methylcyclohexane-toluene-ammonia system from Fenske et al., AIChE Journal, 1,335 (1955), 1955, AIChE
From Separation Process Engineering, Third Edition by Phillip C. Wankat (ISBN: 0131382276) 2012 Pearson Education, Inc. All rights reserved.
check: xA + xB + xC = 1
Read the mole/mass fraction of each component on the axis for that component, using the lines parallel to the edge opposite the corner corresponding to the pure component.
The mixture M lies inside the miscibility boundary, and will spontaneously separate into two phases. Their compositions (E and R) are given by the tie-line through M. region of partial miscibility A-C The compositions of E and R converge at the plait point, P (i.e., no separation).
A 2-component mixture of furfural and water is partially miscible over the composition range from about 8 % furfural to 95 % furfural. Separation by extraction requires a furfural/water ratio in this range (otherwise single phase).
We need to specify only two of the compositions in order to describe each liquid phase completely .
This can be shown on a right-triangle phase diagram, which is easy to plot and read. raffinate compositions are represented by coordinates (xA, xB) extract compositions are represented by coordinates (yA, yB)
Vertical axis corresponds to both xA and yA. Horizontal axis corresponds to both xB and yB
Q: Where does pure C appear on this diagram?
Figure 13-12 Equilibrium for water-chloroform-acetone at 25C and 1 atm From Separation Process Engineering, Third Edition by Phillip C. Wankat (ISBN: 0131382276) Copyright 2012 Pearson Education, Inc. All rights reserved.
More tie-lines can be obtained by trial-anderror, using the conjugate line. Ex.: find the tie-line that passes through M.
Flow rates of E and R are related by mass balance. Compositions of E and R are also related by equilibrium.
Overview of solution using RT diagram: 1. Plot F and S and join with a line. 2. Find mixing point, M, which is co-linear with F and S. 3. Find tie-line through M; find E and R at either end (colinear with M). 4. Find flow rates of E and R.
coord.: (yD,yA)
mixing line
F E M tie-line S
coord.: (xD,xA) R
Co-linearity
F S mixer solve for coordinates of M: (xA,M, xD,M) M
TMB:
F+S=M
xA,M = xD,M =
xA,M - xA,S xD,M - xD ,S =
CMBA: FxA,F + SxA,S = MxA,M = (F + S)xA,M CMBD: FxD,F + SxD,S = MxD,M = (F + S)xD,M
F xA,M - xA,S xD ,M - xD,S = = S xA,F - xA,M xD,F - xD,M
CMBA CMBD
rearrange
Therefore F, S and M are co-linear. To locate M on the FS line: calculate either xA,M or xD,M.
MS
MF
EM
similar triangles
similar triangles
M MR
M=R+E
R xA,M - y A,E ME = = M xA,R - y A,E RE
Your choice! Use mass balances, or measure distances and use lever-arm rule.
E1
each Ri, Si pair creates a mixing line find each Ei, Ri pair using a tie-line
R1 R2
E and R are both points on the equilibrium line. But they are not related by the same tie-line.
Overview of solution using RT diagram: 1. Plot F and S and join with a line. 2. Find mixing point, M, which is colinear with F and S. 3. Plot specified xA,1 on raffinate side of equilibrium line to find R1. 4. Extrapolate R1M line to find EN. 5. Find flow rates of E and R.
mixing line
EN xA,1
M NOT a tie-line
R1
Stage-by-stage analysis
R1 xA,1 1 R2 E1 S = E0 yA,0
stage 1 TMB:
E 0 + R2 = E 1 + R1 E0 R1 = E1 R2 = E2 R3 etc.
constant difference in flow rates of passing streams = Ej Rj+1 = constant stage 1 CMBA: E0yA,0 + R2xA,2 = E1yA,1 + R1xA,1 E0yA,0 R1xA,1 = E1yA,1 R2xA,2 = etc.
F = RN+1 xA,N+1
EN yA,N+1
constant difference in compositions of passing streams net flow of A: xA, = EjyA,j Rj+1xA,j+1 net flow of D: xD, = EjyD,j Rj+1xD,j+1
does not necessarily lie inside the RT graph. All pairs of passing streams Ej, Rj+1 are co-linear with . Using the -point to step off stages on Hunter-Nash diagram: using the specified location of R1 (as xA,1), can find E1 (use tie-line); given the location of E1, can find R2 (use ); given the location of R2, can find E2 (use tie-line); given the location of E2, can find R3 (use ); and so on, until desired separation is achieved.
R1
S = E0
R2
1
extract compositions
A yA xA
1 0 0 xA
P
equilibrium line ends at P
yA 1
0 0
Mixing lines represent passing streams. All mixing lines lie between the limits: (x1, y0) and (xN+1, yN)
EN M D RN+1 R
1
yN
WAIT! In general, operating line is not straight. Plot arbitrary intermediate mixing lines to obtain more points. 1
yA xA
P
(xN+1, yN)
Note: passing streams are (xj+1, yj) instead of (xj, yj+1) as in distillation, simply due to our labeling convention (feed enters at stage N).
0 0 (x1, y0)
A F M Mmin S Mmax D
as M moves towards F, (S/F) decreases before reaching the equilibrium line, there is usually a pinch point (Mmin)
It is not easy to locate this pinch point on a McCabe-Thiele diagram, since the operating line curvature changes as S changes. On a Hunter-Nash diagram, Dmin (corresponding to Mmin) occurs when a mixing line and a tie-line coincide.
min
N,min
8. Connecting R1 and EN,min completes the mass balance 9. Mmin is located at the intersection of SF and R1EN,min
D
min
min
min
N,min
F2
mixer 1
FT
R
F2
E
Feed balance: F1 + F2 = FT
R
N F1 = RN+1
EN
Stage-by-stage analysis: mass balance changes where F2 enters the column upper and lower sections have different sets of operating lines different D-points
F1
EN
S = E0
Stage-by-stage analysis
R1 1 j R F2 k E E0 = S Balance around top of column: R1 E0 = Rj+1 Ej = D1 linear R1, E0, D1 are co-
Balance around bottom of column: EN RN+1 = Ek Rk+1 = D2 RN+1, EN, D2 are co-linear
Overall balance: F2 + RN+1 + E0 = EN + R1 F2 = (EN RN+1) + (R1 E0) = D1 + D2 F2, D1, D2 are co-linear feed-line
R
N F1 = RN+1
D2 is located at the intersection of two mixing lines: RN+1, EN, D2 and F2 , D 1 , D 2 Need another line to locate D1: TMB: FT = F1 + F2 = EN + (R1 E0) = EN + D1 FT, EN, D1 are co-linear D1 is located at the intersection of two mixing lines: R1, E0, D1 and FT, EN, D2
EN
3. Step off stages, initially using D1 to generate the first mixing lines
R1
D2
5. When the tie-line crosses the feed line, the next mixing line will be generated using D2
R2
D1
E2 E1
EN
F1 FT F2
4. Identify the optimum feed stage when the mixing line crosses the feed line, F2D1D2
feed line
How to increase yA,N? need to increase xA,N+1 make RN+1 an reflux stream
makeup solvent
R1 1
E0
extract reflux
R E
(no benefit to raffinate reflux)
F
Turning extract into raffinate : extract is mostly solvent raffinate is mostly diluent We need to remove solvent, e.g., distillation, stripping
R
N RN+1
E
recovered solvent
N F1 = RN+1 xA,N+1
EN yA,N
SR EN
solvent separator
In a conventional liquid-liquid extraction column: reflux yA,N is related by equilibrium to xA,N xA,N depends on xA,N+1 dilute feed gives dilute extract highest yA,N obtained with S Smin , but this requires very large N
PE
product extract
1
L0 D RN+1 Saturated liquid reflux stream is obtained by condensing V1 (vapor stream rich in A) to give L0 (liquid stream rich in A) External reflux ratio = L0/D Internal reflux ratio = L/V
reflux
N EN
recovered solvent
SR
solvent separator
PE
product extract
Extract reflux stream is obtained by removing solvent from EN (extract stream rich in A and solvent) to give RN+1 (raffinate stream rich in A and depleted in solvent) External reflux ratio = RN+1/PE Internal reflux ratio = RN+1/EN
Stage-by-stage balances
Similar to 2-feed liq-liq extraction column: - two D-points (mass balance above and below feed stage) - if F, E0, R1 and RN+1 are specified, same stage-by-stage analysis But RN+1 is an internal stream, usually not specified. Usually specified: F, xA,F, xD,F yA,0, yD,0 xA,1 xA,PE, xD,PE rates) yA,SR, yD,SR RN+1/PE
plot F plot E0 plot R1 on satd raffinate curve plot PE (same location as RN+1 and Q, different flow plot SR
EN = Q + SR = RN+1 + PE + SR
PE A EN SR E0 PE, Q, RN+1 F R1 D
EN is co-linear with Q and SR. EN also lies on satd extract line. Obtain EN/SR from lever-arm rule. We will also need RN+1/SR:
EN RN +1 PE = + +1 SR SR SR dont know
EN SR RN +1 S = + 1+ R SR PE PE PE
RN +1 +1 PE R E P SR N +1 = N - E - 1 = SR SR SR EN PE 1 SR
We dont know the individual flow rates EN, RN+1, but we know EN/SR and RN+1/SR. We can calculate xA,D2 and thereby locate D2 on the ENRN+1 line.
E0
R1