Exercise 1.

Subject: Process for making fluorocarbons.

Given: Flow diagram and a brief description of a fluorocarbons production process in

"Shreve's Chemical Process Industries", 5th ed., by G. T. Austin, pp 353-355.

Find: Draw a process flow diagram and describe the process.

Description of Process: Two main reactions occur:

CCl4 + HF  CCl3F + HCl

CCl3F +HF  CCl2F2 + HCl

Excess carbon tetrachloride is reacted in R1 with HF in the presence of antimony

pentoxide catalyst and a small amount of chlorine to maintain catalyst activity. The HF
contains a small amount of water as an impurity. The effluent from the R1 is HCl,
CCl3F, CCl2F2, unreacted CCl4, and small amounts of water and chlorine. The normal
boiling points in oC of these components in the order of decreasing volatility are:

HCl -84.8
Cl2 -33.8
CCl2F2 -29.8
CCl3F 23.7
CCl4 76.7
H2O 100
 Exercise 1.1 (i) (continued)

The reactor effluent is distilled in D1 to remove the CCl4 as bottoms, which is

recycled to R1. The distillate enters absorber A1, where HCl is absorbed by water to
produce a byproduct of aqueous HCl. The gas from A1 contains residual HCl, which is
neutralized, and chlorine, which is absorbed, by aqueous NaOH, in A2. The effluent
liquid from A2 is waste. Moisture is removed from the gas leaving A2 by absorption
with H2SO4 in A3. The exit liquid from A3 is also waste. The gas leaving A3 is distilled
in D2 to obtain CCl2F2 as a distillate, which is then dried in S1 by adsorption with
activated alumina. Bottoms from D2 is distilled in D3 to recover a distillate of CCl3F,
which is dried with activated alumina in S2. Bottoms from D3, containing residual CCl4,
is recycled to reactor R1.
 Exercise 1.2

Subject: Mixing vs. separation

Given: Thermodynamic principles.

Find: Explanation for why mixing and separation are different.

Analysis: Mixing is a natural, spontaneous process. It may take time, but concentrations
of components in a single fluid phase will tend to become uniform, with an increase in
entropy. By the second law of thermodynamics, a natural process tends to randomness.
The separation of a mixture does not occur naturally or spontaneously. Energy is
required to separate the different molecular species.

Exercise 1.3

Subject: Separation of a mixture requires a transfer of energy to it or the degradation of

its energy.

Given: The first and second laws of thermodynamics.

Find: Explain why the separation of a mixture requires energy.

Analysis: As an example, consider the isothermal minimum (reversible) work of

separation of an ideal binary gas mixture. Therefore, the change in enthalpy is zero.
However, there is a change in entropy, determined as follows. From a chemical
engineering thermodynamics textbook or Table 2.1, Eq. (4):

Wmin   n(h  T0 s)   n(h  T0 s)

out in

R
S c h d iU
V
 RT0
T n
out
k y
i ,k ln yi ,k   n j
in
y
i, j ln yi , j
W
It can be shown that regardless of values of y between 0 and 1, that Wmin is always
positive. This minimum work is independent of the process.
 Exercise 1.4

Subject : Use of an ESA or an MSA to make a separations.

Given: Differences between an ESA and an MSA.

Find: State the advantages and disadvantages of ESA and MSA.

Analysis: With an MSA, an additional separator is needed to recover the MSA. Also,
some MSA will be lost, necessitating the need for MSA makeup. If the MSA is
incompletely recovered, a small amount of contamination may result. The use of an
MSA can make possible a separation that cannot be carried out with an ESA. An ESA
separation is easier to design.

Exercise 1.5

Subject: Producing ethers from olefins and alcohols.

Given: Process flow diagram and for production of methyl tert-butyl ether (MTBE).

Find: List the separation operations.

Analysis: The reactor effluent contains 1-butene, isobutane, n-butane, methanol, and
MTBE. The separation steps are as follows:

Separation Step Products

Distillation Distillate: all C4s, methanol

Bottoms: 99 wt% MTBE

L/L Extraction with water Extract: methanol, water

Raffinate: C4s

Distillation Distillate: methanol to recycle

Bottoms: water for recycle
 Exercise 1.6

Subject: Conversion of propylene to butene-2s.

Given: Process flow diagram and for production of butene-2s.

Find: List the separation operations.

Analysis: The reactor effluent contains ethylene, propylene, propane, butene-2s, and
C5+. The separation steps are as follows:

Separation Step Products

Distillation Distillate: ethylene

Sidestream: propylene, propane
Bottoms: butene-2s, C5+

Distillation Distillate: propylene

Bottoms: propane

Distillation Distillate: butene-2s

Bottoms: C5+

Exercise 1.7

Subject: Use of osmosis for separating a chemical mixture.

Given: The definition of osmosis.

Find: Explain why osmosis cannot be used for separating a mixture.

Analysis: Osmosis is the transfer of a solvent through a membrane into a mixture of

solvent and solute. Thus, it is a mixing process, not a separation process.
 Exercise 1.8

Subject: Osmotic pressure for the separation of water from sea water by reverse osmosis
with a membrane.

Given: Sea water containing 0.035 g of salt/cm3 of sea water on one side of a membrane
Molecular weight of the salt = 31.5
Temperature = 298 K
Pure water on the other side of a membrane

Find: Minimum required pressure difference in kPa across the membrane

Analysis: The minimum pressure difference across the membrane is equal to the osmotic
pressure of the sea water, since the osmotic pressure of pure water on the other side is
zero. The equation given for osmotic pressure is =RTc/M.

R = 8.314 kPa-m3/kmol-K
T = 298 K
c = 0.035 g/cm3 = 35 kg/m3
M = 31.5 kg/kmol

Minimum pressure difference across a membrane =


 8.314   298   35  2, 750 kPa
31.5
 Exercise 1.9

Subject: Use of a liquid membrane to separate the components of a gas mixture

Given: A liquid membrane of ethylenediaminetetraacetic acid, maintained between two

sets of microporous, hydrophobic hollow fibers, packed into a cell, for removing sulfur
dioxide and nitrogen oxides from flue gas.

Required: A sketch of the membrane device.

Analysis: A sweep fluid is generally required. In some cases, a vacuum could be pulled
on the permeate side. The membrane device is shown below.
 Exercise 1.10

Wanted: The differences, if any, between adsorption and gas-solid chromatography.

Analysis: Adsorption can be conducted by many techniques including fixed bed, moving
bed, slurry, and chromatography. In chromatography, unlike the other adsorption
techniques, an eluant is used to carry the mixture through the tube containing the sorbent.
Multiple pure products are obtained because of differences in the extent and rate of
adsorption, resulting in different residence times in the tube. The tube is made long
enough that the residences do not overlap.

Exercise 1.11

Wanted: Is it essential in gas-liquid chromatography that the gas flows through the
packed tube in plug flow?

Analysis: Plug flow is not essential, but it can provide sharper fronts and, therefore, the
chromatographic columns can be shorter.

Exercise 1.12

Wanted: The reason why most small particles have a negative charge.

Analysis: Small particles can pick up a negative charge from collisions in glass ware. In
an aqueous solution, inorganic and polar organic particles develop a charge that depends
on the pH of the solution. The charge will be negative at high pH values.

Exercise 1.13

Wanted: Can a turbulent-flow field be used in field-flow fractionation?

Analysis: Field-flow fractionation requires a residence-time distribution of the

molecules flowing down the tube. This is provided best by laminar flow. The residence-
time distribution with turbulent flow is not nearly as favorable. Turbulent flow would not
be practical.
 Exercise 1.14

Subject: Sequence of three distillation columns in Fig. 1.9 for separating light
hydrocarbons.

Given: Feed to column C3 is stream 5 in Table 1.5. Alter the separation to produce a
distillate containing 95 mol% iC4 at a recovery of 96%.

Find: (a) Component flow rates in the distillate and bottoms from column C3.
(b) Percent purity of nC4 in the bottoms.
(c) Percent recovery of iC4, for 95 mol% iC4 in the distillate, that will
maximize the percent purity of nC4 in the bottoms.

Assumptions: Because of the relatively sharp separation in column C3 between iC4 and
nC4, assume that all propane in the feed appears in the distillate and all C5s appear in the
bottoms.

Analysis: (a) Isobutane to the distillate = (0.96)(171.1) = 164.3 lbmol/h

Total distillate rate = 164.3/0.95 = 172.9 lbmol/h
Normal butane to the distillate = 172.9 - 2.2 - 164.3 = 6.4
Material balance around column C3, in lbmol/h:
Component Feed Distillate Bottoms

Propane 2.2 2.2 0.0

Isobutane 171.1 164.3 6.8
Normal butane 226.6 6.4 220.2
Isopentane 28.1 0.0 28.1
Normal pentane 17.5 0.0 17.5
Total 445.5 172.9 272.6

(b) % Purity of nC4 in bottoms = (220.2/272.6) x 100% = 80.8%

(c) Let x = lbmol/h of nC4 in the distillate
y = lbmol/h of iC4 in the distillate
P = mole fraction purity of nC4 in the bottoms

226.6  x 226.6  x
P  (1)
.  y )  (226.6  x )  281
(1711 .  17.5 443.3  y  x
y
Fractional purity of iC 4 in the distillate =  0.95 (2)
2.2 + y + x
Combining (1) and (2) to eliminate x, and optimization of P with respect to y gives:
P = 0.828 or 82.8 mol% nC4 in the bottoms, x = 6.8 lbmol/h, y = 171.1 lbmol/h
Therefore, 100% recovery of iC4 in the distillate maximizes the purity of nC4 in the
bottoms.
 Exercise 1.15

Subject: Sequence of two distillation columns, C1- C2, for the separation of alcohols.

Given: 500 kmol/h feed of 40% methanol (M), 35% ethanol (E), 15% isopropanol (IP),
and 10% normal propanol (NP), all in mol%. Distillate from column C1 is 98 mol% M,
with a 96% recovery. Distillate from column C2 is 92 mol% E, with a recovery of 95%
based on the feed to column C1.

Find: (a) Component flow rates in the feed, distillates and bottoms.
(b) Mol% purity of combined IP and NP in the bottoms from column C2.
(c) Maximum achievable purity of E in the distillate from column C2 for 95%
recovery of E from the feed to column C1.
(d) Maximum recovery of E from the feed to column C1 for a 92 mol% purity of
E in the distillate from column C2.

Assumptions: Because of the sharp separation in column C1, neglect the presence of
propanols in the distillate from column C1. Neglect the presence of M in the bottoms
from column C2. The distillate from C2 does not contain normal propanol.

Analysis: (a) M in distillate from C1 = (0.96)(500)(0.40) = 192 kmol/h

Total distillate from C1 = 192/0.98 = 195.92 kmol/h
E in distillate from C1 = 195.92 - 192 = 3.92 kmol/h
E in feed to C2 = (500)(0.35) - 3.92 = 171.08 kmol/h
M in feed to C2 = M in distillate from C2 = (500)(0.40) - 192 = 8 kmol/h
E in distillate from C2 = (500)(0.35)(0.95) = 166.25 kmol/h
Total distillate from C2 = 166.25/0.92 = 180.71 kmol/h
IP in distillate from C2 = 180.71 - 166.25 - 8 = 6.46 kmol/h
Block flow diagram:
 Exercise 1.15 (continued)

Analysis: (a) continued

Material balance table (all flow rates in kmol/h):

Component Stream 1 2 3 4 5
M 200 192.00 8.00 8.00 0.00
E 175 3.92 171.08 166.25 4.83
IP 75 0.00 75.00 6.46 68.54
NP 50 0.00 50.00 0.00 50.00
Total 500 195.92 304.08 180.71 123.37

The assumption of negligible NP in stream 4 is questionable and should be corrected

when designing the column.

(b) Mol% purity of (IP + NP) in bottoms of C2 = (68.54 + 50.00)/123.37 or

96.08%

(c) If the overall recovery of E in the distillate from C2 is fixed at 95%, the
maximum purity of E in that distillate occurs when no propanols appear in that distillate.
Then,
mol% purity of E = 100% x 166.25/(166.25 + 8.0) = 95.41%

(d) The maximum recovery of E in the distillate from C2 occurs when E does not
appear in the bottoms from C2. Thus, that maximum is 100% x (171.08/175) = 97.76%
 Exercise 1.16

Subject: Pervaporation for the partial separation of ethanol and benzene

Given: 8,000 kg/h of 23 wt% ethanol and 77 wt% benzene. Polymer membrane is
selective for ethanol. Permeate is 60 wt% ethanol. Retentate is 90 wt% benzene.

Find: (a) and (b) Component flow rates in feed, permeate, and retentate on a diagram.
(c) Method to further separate the permeate.

Analysis: (a) and (b) Let: P = permeate flow rate

R = retentate flow rate
Total material balance: 8,000 = P + R (1)
Ethanol material balance: 8,000(0.23) = (0.60) P + (0.10) R (2)
Solving (1) and (2) simultaneously, P = 2,080 kg/h and R = 5,920 kg/h

The resulting material balance and flow diagram is:

(c) Gas adsorption, gas permeation, or distillation to obtain ethanol and the azeotrope,
which can be recycled.
 Exercise 1.17

Subject: Separation of hydrogen from light gases by gas permeation with hollow fibers.

Given: Feed gas of 42.4 kmol/h of H2, 7.0 kmol/h of CH4, and 0.5 kmol/h of N2 at 40oC
and 16.7 MPa. Retentate exits at 16.2 kPa and permeate exits at 4.56 kPa. Gas heat
capacity ratio =  = 1.4.

Assumptions: Membrane is not permeable to nitrogen. Reversible gas expansion with

no heat transfer between the retentate and permeate. Separation index is based on mole
fractions.

Find: (a) Component flows in the retentate and permeate if the separation index, SP, for
hydrogen relative to methane is 34.13, and the split fraction (recovery), SF, for hydrogen
from the feed to the permeate is 0.6038.
(b) Percent purity of hydrogen in the permeate.
(c) Exit temperatures of the retentate and permeate.
(d) Process flow diagram with complete material balance

Analysis: (a) and (d)

Hydrogen in permeate = (0.6038)(42.4) = 25.6 kmol/h
Hydrogen in retentate = 42.4 - 25.6 = 16.8 kmol/h
Let: x = kmol/h of methane in permeate
Then, 7.0 - x = kmol/h of methane in retentate
From Eq. (1-4),
25.6 / 16.8
SP  34.13  (1)
x / (7  x )
Solving (1), x = 0.3 kmol/h of methane in the permeate
Methane in the retentate = 7.0 - 0.3 = 6.7 kmol/h
The resulting material balance and flow diagram is:
 Exercise 1.17 (continued)

Analysis: (continued)

(b) Percent purity of hydrogen in permeate = 100% x 25.6/25.9 = 98.8%

(c) For reversible adiabatic (isentropic) expansion, assuming an ideal gas,

the final temperature is given from thermodynamics by:

FP I
 1

TG J

(2)
HP K
out
Tout 1
1

where subscript 1 refers to upstream side, subscript out refers to downstream side, both
temperature and pressure are absolute, and  is the gas heat capacity ratio.
For both the retentate and the permeate, T1 = 40oC = 313 K and P1 =16.7 MPa.

For the retentate, Pout = P3 = 16.2 MPa. From (2),

1.4 1
 16.2  1.4
Tout  T3  313    310 K = 37 o C
 16.7 

For the permeate, P2 = 4.56 MPa. From (2),

1.4 1
 4.56  1.4
T2  313    216 K=  57 o C
 16.7 
 Exercise 1.18

Subject: Natural gas is produced when injecting nitrogen into oil wells. The nitrogen is
then recovered from the gas for recycle.

Given: 170,000 SCFH (60oF and 14.7 psia) of gas containing, in mol%, 18% N2, 75%
CH4, and 7% C2H6 at 100oF and 800 psia. Recover the N2 by gas permeation followed by
adsorption.
The membrane is selective for nitrogen. The adsorbent is selective for methane. The
adsorber operates at 100oF, and 275 psia during adsorption and 15 psia during
regeneration. Permeate exits the membrane unit at 20oF and a low pressure. Two stages
of compression with cooling are needed to deliver the permeate gas to the adsorber. The
regenerated gas from the adsorber is compressed in three stages with cooling, and is
combined with the retentate to give the natural gas product.

Assumptions: The membrane is not permeable to ethane. The separation index, SP,
defined by Eq. (1-4), is applied to the exiting retentate and permeate.

Find: (a) Draw a labeled process flow diagram.

(b) Compute the component material balance, based on the following data:
Separation index, SP, for the membrane = 16 for nitrogen relative to methane. The
adsorption step gives 97 mol% methane in the adsorbate with an 85% recovery based on
the feed to the adsorber. The pressure drop across the membrane is 760 psi. The
retentate exits at 800 psia.
The combined natural gas product contains 3 mol% nitrogen. Place the results of the
material balance in a table.

Analysis: (b) Refer to the process flow diagram on next page for stream numbers.
Let: ai = molar flow rate of N2 in lbmol/h in stream i.
bi = molar flow rate of CH4 in lbmol/h in stream i
ci = molar flow rate of ethane in lbmol/h in stream i
Feed flow rate = 170,000 SCFM / 379 SCF/lbmol at SC = 448.5 lbmol/h
a1 = 0.18(448.5) = 80.7, b1 = 0.75(448.5) = 336.4, c1 = 0.07(448.5) = 31.4
Because ethane does not permeate through the membrane, c3 = c6 = 31.4
and c2 = c4 = c5 = 0
Solve for a2, a3, a4, a5, a6, and b2, b3, b4, b5, b6 from 10 equations in 10 unknowns.
Membrane selectivity:
a2 / a3
SP  16  (1)
b2 / b3
Component balances around the membrane unit:
a2 + a3 = 80.7 b2 + b3 = 336.4
Component balances around the adsorber:
a2 = a4 + a5 b2 = b4 + b5
 Exercise 1.18 (continued)

Component balances around the line mixer that mixes retentate with adsorbate gas:
a6 = a3 + a5 b6 = b3 + b5
Methane purity in the adsorbate:
b5 = 0.97(b5 + a5)

Find: (b) (continued)

Methane recovery: b5 = 0.85 b2

Mol% nitrogen in the final natural gas: a6 = 0.03(a6 + b6 + 31.4)

All equations are linear except (1). Solving these 10 equations with a nonlinear equation
solver, such as in the Polymath program, results in the following material balance table:

Flow rate, lbmol/h

Component Stream 1 2 3 4 5 6
Nitrogen 80.7 73.3 7.4 69.9 3.4 10.8
Methane 336.4 128.7 207.7 19.3 109.4 317.1
Ethane 31.4 0.0 31.4 0.0 0.0 31.4
Total 448.5 202.0 246.5 89.2 112.8 359.3

(a) Labeled process flow diagram

 Exercise 1.19

Subject: Suitable distillation sequence and all alternative distillation sequences

Given: The following feed to a distillation sequence:

Component Feed rate, Normal

kmol/h boiling
point, K
Methane 19 112
Benzene 263 353
Toluene 85 384
Ethylbenzene 23 409

Assumptions: Applicability of distillation heuristics in Section 1.7.

Find: (a) A suitable distillation sequence of 3 columns. (b) All possible sequences of 4
columns for the separation of a 5-component feed.

Analysis: (a) The feed components are already ordered by volatility. The most
applicable heuristic of Section 1.7 is: Remove, early in the sequence, those components
of greatest molar percentage in the feed. This is because the amount of benzene in the
feed greatly exceeds that of the other three components. Applying this heuristic to the
first column, separate between benzene and toluene. Then, in the remaining two columns
in parallel, separate the two resulting binary mixtures. Thus, a reasonable sequence is:

Methane

Benzene
Toluene

Ethylbenzene

Exercise 1.19 Continued

The above sequence can also be written in the following shorthand notation using the first
letter of the name of each component:

MBTE MT/BE M/T B/E

(b) For 5 products, A, B, C, D, and E, 4 distillation columns are needed and 14

alternative sequences are possible, as follow using shorthand notation:
 Exercise 1.20

Subject: Separation processes for bioproducts

Given: The need to design a bioseparation operation to distinguish a protein, nucleic

acid, or viral gene vector

Assumptions: none

Find:
(a) five physical and biochemical features of these biological species by which
they could be distinguished in a bioseparation
(b) a bioseparation operation that could be used to selectively remove or retain
each species from a mixture of the other two
(c) Summarize important considerations in maintaining the activity of each species
that would constrain the operating parameters of each bioseparation.
(d) List the purity requirements required for FDA approval of the purified species
as a parenteral product.

Analysis:
(a) Properties that could allow separation: density, size, solubility, charge,
hydrophobicity.
(b) Separation operations: CsCl gradient ultracentrifugation (UC) selectively retains
viral vectors from proteins and nucleic acids based primarily on density.
Ultrafiltration (UF) is commonly used to size-selectively remove nucleic acids
enzymatically digested by nuclease (e.g. BenzonaseTM) from proteins and viral
vectors. Ion-exchange adsorption (IEX) is used to selectively remove proteins
and/or nucleic acids from viral suspensions (or vice-versa).
(c) Some important considerations in UC, UF and IEX are maintaining temperature
(~4oC), water activity (i.e. ionic strength), and pH to preserve virus stability,
proper materials selection to limit biological reactivity of equipment surfaces to
prevent protein denaturation or virus disassembly, and employing aseptic
operating procedures to prevent batch contamination.
(d) The Center for Biologics Evaluation and Research (CBER) of the Food and Drug
Administration (FDA) approves HCP limits established by the manufacturer after
review of process capability and safety testing in toxicology and clinical trials.
The World Health Organization (WHO) sets DNA levels at  10 g per dose.
Less than 1 virus particle per 106 doses is allowed in rDNA-derived protein
products.
 Exercise 1.21

Subject: Separation processes for bioproducts from E. coli

Given: The need to design a bioseparation operation to distinguish a protein, nucleic

acid, or viral gene vector from E. coli.

Assumptions: Overexpression of non-secreted heterologous protein product that is not

found as an inclusion body.
Find: (a) primary structures and components of E.coli that must be removed from a
fermentation broth to purify a heterologous protein product expressed for
pharmaceutical use.
(b) a sequence of steps to purify a conjugate heterologous protein that
remained soluble in cell paste.
(c) a separation operation for each step in the process and list one alternative
for each step.
(d) important considerations in establishing operating procedures to preserve
the activity of the protein.
(e) the overall yield of the process, and the scale of operation required to
produce 100 kg per year of the protein at a titer of 1 g/L, if net yield in each
step in your process was 80%.
Analysis:
(a) Must remove biopolymers (carbohydrates, fats, nucleic acids, and proteins besides
target protein) and particulates (cell fragments of membrane, peptidoglycan,
organelles, etc).
(b) and (c): fluid/solid separation of cells from broth by tangential flow filtration or
centrifugal precipitation; homogenization to release heterologous protein by
Gaulin press or sonication; fluid/solid separation of cell debris from broth by
direct-flow filtration or centrifugal precipitation; solute-solute separation of
biopolymers from target by ultrafiltration and/or chromatography; formulation
using direct-flow filtration with a 0.22 micron filtration to remove bioburden, and
tangential flow filtration to introduce formulation buffer.
(d) Some important considerations in UC, UF and IEX are maintaining temperature
(~4oC), water activity (i.e. ionic strength), and pH to preserve protein stability,
proper materials selection to limit biological reactivity of equipment surfaces to
prevent protein denaturation, and employing aseptic operating procedures to
prevent batch contamination.
(e) For 5 step-process, overall yield = 0.8^5 = 0.33 or 33%. Scale of operation is
calculated by: 100 kg/yr * 1 yr/50 process weeks * 1 week/ 2 batch * 1 L/0.001 kg
* 1 kg/0.33 recovered kg = 3030 L/batch at a rate of 2 batches per week.
 Exercise 1.22

Subject: Purification process for adeno-associated viral vector from anchorage-

dependent mammalian cell line.

Given: The need to design a bioseparation operation to distinguish adeno-associated viral

vector from anchorage-dependent mammalian cell line.

Assumptions: none
Find:
(a) Primary structures and components of the mammalian cell line that must be
removed from a cell culture broth to purify a viral vector propagated for
pharmaceutical use.
(b) A sequence of steps to purify the viral vector that remained soluble in cell lysate.
(c) A separation operation for each step in the process and list one alternative for
each step.
(d) Important considerations in establishing operating procedures to preserve the
activity of viral vector.
(e) The overall yield of the process, and the scale of operation required to produce
100 kg per year of the virus at a titer of 1 g/L, if net yield in each step in your
process was 80%.
Analysis:
(a) Must remove biopolymers (carbohydrates, fats, nucleic acids, and proteins
besides target protein) and particulates (cell fragments of membrane, peptidoglycan,
organelles, etc).
(b) and (c) fluid/solid separation of cells from broth by tangential flow filtration; lysis
of mammalian cell to release virus by freeze-thaw; fluid/solid separation of cell debris
from broth by direct-flow filtration or centrifugal precipitation; solute-solute separation
of biopolymers from target by ultrafiltration and/or chromatography; formulation using
direct-flow filtration with a 0.22 micron filtration to remove bioburden, and tangential
flow filtration to introduce formulation buffer.
(d) Some important considerations in UC, UF and IEX are maintaining temperature
(~4oC), water activity (i.e. ionic strength), and pH to preserve virus stability, proper
materials selection to limit biological reactivity of equipment surfaces to prevent viral
degradation, and employing aseptic operating procedures to prevent batch contamination.
(e) For 5 step-process, overall yield = 0.8^5 = 0.33 or 33%. Scale of operation is
calculated by: 100 kg/yr * 1 yr/50 process weeks * 1 week/ 2 batch * 1 L/0.001 kg * 1
kg/0.33 recovered kg = 3030 L/batch at a rate of 2 batches per week.
 Exercise 1.23

Subject: Separation of a mixture of ethylbenzene, o-xylene, m-xylene, and p-xylene

Find: (a) Reason why distillation is not favorable for the separation of m-xylene from
p-xylene.
(b) Properties of m-xylene and p-xylene for determining a means of separation.
(c) Why melt crystallization and adsorption can be used to separate m-xylene
from p-xylene.

Analysis: (a) In the order of increasing normal boiling point:

Component nbp, oR Relative

volatility
Ethylbenzene 737.3
1.08
Paraxylene 741.2
1.02
Metaxylene 742.7
1.16
Orthoxylene 751.1

From the values of relative volatility, the separation of p-xylene from m-xylene by
distillation is not practical. The other two separations are practical by distillation, but
require large numbers of stages.

(b) From Reference 10, the following properties are obtained:

Property m-xylene p-xylene

Molecular weight 106.167 106.167
van der Waals volume, m3/kmol 0.07066 0.07066
van der Waals area, m2/kmol x 10-8 8.84 8.84
Acentric factor 0.3265 0.3218
Dipole moment, debye 0.30 0.00
Radius of gyration, m x 1010 3.937 3.831
Normal melting point, K 225.3 286.4
Normal boiling point, K 412.3 411.5
Critical temperature, K 617 616.2
Critical pressure, MPa 3.541 3.511

From the table, the difference of 61.1 K in melting points is very significant and can be
exploited in melt crystallization. The difference in dipole moments of 0.30, while not
large, makes possible the use of adsorption or distillation with a solvent

(c) Explanations are cited in Part (b).

 Exercise 1.24

Subject: Separation of a near-azeotropic mixture of ethyl alcohol and water.

Given: A list of possible methods to break the azeotrope.

Find: Reasons why the following separation operations might be used:

(a) Extractive distillation
(b) Azeotropic distillation
(c) Liquid-liquid extraction
(d) Crystallization
(e) Pervaporation membrane
(f) Adsorption

Analysis:
Pertinent Properties:

Property Ethanol Water

Melting point, oC -112 0
Dipole moment, debye 1.69 1.85

(a) Extractive distillation is a proven process using ethylene glycol.

(b) Heterogeneous azeotropic distillation is possible with benzene, carbon
tetrachloride, trichloroethylene, and ethyl acetate.
(c) Liquid-liquid extraction is possible with n-butanol.
(d) Crystallization is possible because of the large difference in the melting
points.
(e) Pervaporation is possible using a polyvinylalcohol membrane.
(f) Adsorption is possible using silica gel or activated alumina to adsorb the
water.
 Exercise 1.25

Subject: Removal of ammonia from water.

Given: 7,000 kmol/h of water containing 3,000 ppm by weight of ammonia at 350 K
and 1 bar.

Find: A method to remove the ammonia.

Analysis: From Perry's Handbook, 7th edition, page 2-87, the volatility of ammonia is
much higher than that of water. Therefore, could use distillation or air stripping. Also,
could adsorb the ammonia on a carbon molecular sieve or use a liquid organic membrane
containing an acidic complexing agent to form an ion-pair with the ammonia ion, NH4+.
 Exercise 1.26

Subject: Separation of a mixture by a sequence of distillation columns.

Given: Feed stream containing in kmol/h: 45.4 C3, 136.1 iC4, 226.8 nC4, 181.4 iC5,
and 317.4 nC5. Three columns in series, C1, C2, and C3. Distillate from C1 is C3-rich
with a 98% recovery. Distillate from C2 is iC4-rich with a 98% recovery. Distillate from
C3 is nC4-rich with a 98% recovery. Bottoms from C3 is C5s-rich with a 98% recovery.

Find: (a) Process-flow diagram like Figure 1.8.

(b) Material-balance table like Table 1.5.
(c) Mole % purities in a table like Table 1.7

Assumptions: Reasonable values for splits of iC4 to streams where they are not the
main component.

Analysis:
(a) Process-flow diagram:

2 4 6

C C C
1 1 2 3

3 5

7
 Exercise 1.26 (continued)

(b) Using given recoveries:

Propane in Stream 2 = 0.98(45.4) = 44.5 kmol/h
i-Butane in Stream 4 = 0.98(136.1) = 133.4 kmol/h
n-Butane in Stream 6 = 0.98(226.8) = 222.3 kmol/h
C5s in Stream 7 = 0.98(181.4 + 317.5) = 488.9 kmol/h

Material-balance table in kmol/h:

Comp 1 2 3 4 5 6 7
C3 45.4 44.5 0.9 0.9 0.0 0.0 0.0
iC4 136.1 1.3 134.8 133.4 1.4 1.4 0.0
nC4 226.8 0.5 226.3 2.5 223.8 222.3 1.5
iC5 181.4 0.0 181.4 0.0 181.4 7.0 174.4
nC5 317.5 0.0 317.5 0.0 317.5 3.0 314.5
Total 907.2 46.3 860.9 136.8 724.1 233.7 490.4

(c) Mol% purity of propane-rich product = 45.4/46.3 = 0.961 = 96.1%

Mol% purity of i-butane-rich product = 133.4/136.8 = 0.975 = 97.5%
Mol% purity of n-butane-rich product = 222.3/233.7 = 0.951 = 95.1%
Mol% purity of C5s-rich product = (174.4 + 314.5)/490.4 = 0.997 = 99.7%
 Exercise 1.27

Subject: Methods for removing organic pollutants from wastewater.

Given: Available industrial processes:

(1) adsorption
(2) distillation
(3) liquid-liquid extraction
(4) membrane separation
(5) stripping with air
(6) stripping with steam
Find: Advantages and disadvantages of each process.

Analysis:
Some advantages and disadvantages are given in the following table:

Method Advantages Disadvantages

Adsorption Adsorbents are available. Difficult to recover pollutant.
Best to incinerate it.
Distillation May be practical if pollutant is Impractical is water is more
more volatile. volatile.
L-L extraction Solvent are available. Water will be contaminated with
solvent.
Membrane May be practical if a membrane May need a large membrane area
can be found that is highly if water is the permeate.
selective for pollutant.
Air stripping May be practical if pollutant is Danger of producing a flammable
more volatile. gas mixture.
Steam stripping May be practical if pollutant is Must be able to selectively
more volatile. condense pollutant from
overhead.

With adsorption, can incinerate pollutant, but with a loss of adsorbent.

With distillation, may be able to obtain a pollutant product.
With L-L extraction, will have to separate pollutant from solvent.
With a membrane, may be able to obtain a pollutant product.
With air stripping, may be able to incinerate pollutant.
With steam stripping may be able to obtain a pollutant product.
 Exercise 1.28

Subject: Removal of VOCs from a waste gas stream.

Given: Waste gas containing VOCs that must be removed by any of the following
methods:
(1) absorption
(2) adsorption
(3) condensation
(4) freezing
(5) membrane separation

Find: Advantages and disadvantages of each method.

Analysis:
Some advantages and disadvantages are given in the following table:

Method Advantages Disadvantages

Absorption Good absorbents probably exist. Absorbent may stripped into the
waste gas.
Adsorption Good adsorbents probably exist. May have to incinerate the spent
adsorbent.
Condensation May be able to recover the VOC May require high pressure and/or
as a product. low temperature.
Freezing May be able to recover the VOC May require a low temperature.
as a product.
Membrane May be able to recover the VOC May be difficult to obtain high
as a product. selectivity. May require a very
high pressure.

With absorption, may be able to distil the VOC from the absorbent.
With adsorption, may be able to incinerate the VOC or recover it.
With condensation, can recover the VOC as a product.
With freezing, can recover the VOC as a product.
With a membrane, can recover the VOC as a product.

The process shown on the following page shows a process for recovering acetone from
air. In the first step, the acetone is absorbed with water. Although water is far from
being the most ideal solvent because of the high volatility of acetone in water, the air will
not be contaminated with an organic solvent. The acetone-water mixture is then easily
separated by distillation, with recycle of the water.
 Exercise 1.28 (continued)

One possible process-flow diagram:

Clean gas Makeup

Water Acetone

Absorber
Distillation

Gas Feed

Recycle Water
 Exercise 1.29

Subject: Separation of air into nitrogen and oxygen.

Given: Air to be separated.

Find: Three methods for achieving the separation.

Analysis: Three methods are used commercially for separating air into oxygen and
nitrogen:
1. Gas permeation mainly for low capacities
2. Pressure-swing gas adsorption for moderate capacities.
3. Low-temperature distillation for high capacities.

Exercise 1.30

Subject: Separation of an azeotropic mixture of water and an organic compound.

Given: An azeotropic mixture of water and an organic compound such as ethanol.

Find: Suitable separation methods.

Analysis:
Several suitable methods are:
Pervaporation
Heterogeneous azeotropic distillation
Liquid-Liquid extraction.

Exercise 1.31

Subject: Production of magnesium sulfate from an aqueous stream.

Given: An aqueous stream containing 5 wt% magnesium sulfate.

Find: Suitable process for producing nearly pure magnesium sulfate.

Analysis: Use evaporation to a near-saturated solution, followed by crystallization to

produce a slurry of magnesium sulfate heptahydrate crystals. Use a centrifuge or filter to
remove most of the mother liquor from the crystals, followed by drying. A detailed flow
sheet of the process is shown and discussed near the beginning of Chapter 17.
 Exercise 1.32

Subject: Separation of a mixture of acetic acid and water.

Given: A 10 wt% stream of acetic acid in water

Find: A process that may be more economical than distillation.

Analysis: The solution contains mostly water. Because water is more volatile than
acetic acid, distillation will involve the evaporation of large amounts of water with its
very high enthalpy of vaporization. Therefore, it is important to consider an alternative
method such as liquid-liquid extraction. Such a process is shown and discussed near the
beginning of Chapter 8.

Exercise 1.33

Subject: Separation by distillation of an aqueous solution of bioproducts

Given: The following clarified fermentation broth feed at 37oC and 1 atm:

Component Conc., g/L water Normal B.Pt., oC Min. Product

Purity
Acetone 9.9 56.5 90%
Ethanol 19.8 78.4 90%
Water 55.1 100 -
n-Butanol 3.3 117 99.5%

Assumptions: Ideal solutions (actually a very bad assumption).

Find: A suitable distillation sequence using the heuristics of Section 1.7.

Analysis: Based on data in the above table, water is in the largest amount and should be
removed early in the sequence. n-butanol is the highest purity and should be removed
last in the sequence. Applying the heuristics of Section 1.7, separate between ethanol and
water in the first column. Then separate the two binary mixtures, acetone-ethanol and
water-butanol.