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CHAPTER 6 SOLUTIONS

6.1 From the Chemical Market Reporter, Aug. 17, 1998

Price, $/lb MW, lb/lbmol


Ethylene 0.215 28.05
Ethylene glycol 0.26 62.07
NaOH 1.70 40.08
Cl2 0.128 70.91

Conventional reaction path: C2H4 + 1/2 O2 + H2O → CH2(OH)CH2(OH)

Assuming negligible cost for O2, H2O:

28.05
Economic potential per lb EG = 1 x 0.26 - x 0.215 = $0.163/lb EG
62.07

Using NaOH, Cl2: C2H4 + Cl2 + 2NaOH → CH2(OH)CH2(OH) + 2NaCl

Assuming negligible value for the product NaCl:

70.91 2 ( 40.08)
Economic potential = 0.163 - x 0128
. − x1.70 = - $2.173/lb EG
62.07 62.07

For this reaction path to be viable, cheap sources of NaOH and Cl2
and/or a demand for NaCl, at a fairly high price, are necessary.

SM-6-1
6.2 a. The following vapor pressures were graphed using ASPEN PLUS. The
graph can be reproduced using the file EXER6-2.bkp in the ASPEN folder,
under Computer Solution Files, associated with the Solution Manual on the
Wiley web site for this book.
PL vs Temperature
250

LIQUID 1-BUTENE
LIQUID 1,3-BUTA
200

LIQUID CIS-2-BU
LIQUID ETBE
150
PL psi
100
50

0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160 170 180 190 200
Temperature F

As in Example 6.2, ETBE is much less volatile than the other species.
Hence, the conclusions are identical.

b. In one distribution of chemicals, as illustrated below, ethanol is fed to the


reactive distillation column near the top, above the trays containing catalyst.
The mixed-C4 stream is fed below the reacting section. ETBE, the least
volatile species, concentrates in the bottoms product, along with unreacted
ethanol. During process synthesis, it is reasonable to provide a small excess
of 1-butene and to assume that the ethanol is completely consumed. The
lighter C4 compounds concentrate in the distillate.
Unreacted C4’s

Ethanol

Catalyst
Section

Mixed-C4
stream

ETBE
Ethanol

SM-6-2
6.3 ASPEN PLUS Flowsheet – simulation results can be reproduced using the file
EXER6.3.bkp in the ASPEN folder, under Computer
Solution Files, associated with the Solution Manual on
the Wiley web site for this book.

SP1

S6 PURGE
C2

S5
S2A
H1 F1
S7
M2 S4

FEED R1 PROD

S2B

Calculation Sequence

SEQUENCE USED WAS:


$OLVER01 H1 F1 SP1 C2 *R1 M2
(RETURN $OLVER01)

Tabulated Results

Purge/Recycle PROD Recycle Purge Purge Purge


Ratio Flow Rate Flow Rate Flow Rate Mole Fraction Mole Fraction
(lbmol/hr) (lbmol/hr) (lbmol/hr) Ar CH4
0.1 40.67 165.0 18.32 0.033 0.060
0.08 41.61 189.5 16.48 0.036 0.067
0.06 42.63 226.8 14.47 0.041 0.076
0.04 43.75 294.4 12.27 0.049 0.090
0.02 45.05 476.8 9.73 0.062 0.113

Care should be exercised in interpreting these results as ASPEN PLUS


reported convergence errors at each purge/recycle ratio. As expected,
at the elevated pressure (as compared with Example 6.4), the conversion to
product is higher, the recycle flow rate is reduced, as is the purge flow rate.
Also, as expected, the mole fractions of Ar and CH4 in the purge stream are
increased.

SM-6-3
6.4

Alternative 1

The CHEMCAD simulator is used to make the material balance with following
process topology (flowsheet, where negative numbers are streams out) based on Fig. 6.18.

Equipment No. Equipment Model Equipment Name Stream Numbers


1 MIXE Mixer 1 2 14 20 -4
2 CONT H2 cont 4 -15
3 REAC reac1 15 -5
4 GIBS reac2 5 -6
5 FLAS flash 6 -7 -8
6 DIVI purge 7 -9 -10
8 CSEP sep1 8 -11 -12
9 CSEP sep2 12 -13 -17
10 CSEP sep3 17 -14 -18
11 COMP comp1 10 -20

Note the use of two reactor models in series. The first reactor, reac1 modeled by
REAC, converts 70% of the toluene to benzene by the irreversible reaction:

H2 + C7H8 → CH4 + C6H6

The H2-to-toluene molar ratio in the feed to reac1 is specified as 4. This is established by
the feedback controller, H2 cont, modeled by CONT, which adjusts the flow rate of the
makeup H2, Stream 2. The second reactor, reac2, modeled by GIBS, takes the reactor
effluent from reac1 to chemical equilibrium at 1,000oF and 520 psia. The only components
allowed to take part in establishing chemical equilibrium in reac2 are H2, benzene, and
biphenyl, which react by the reversible reaction:

2 C6H6 ↔ C12H10 + H2

At 1,000oF and 520 psia, the equilibrium conversion of benzene to biphenyl is small, of
the magnitude of 2%.

The flash, modeled by FLAS, is an isothermal flash at a temperature of 100oF and


a pressure of 500 psia. The flash vapor, Stream 7, is sent to the purge unit, modeled by
DIVI, where 25% of the vapor is purged to Stream 9, with the balance recycled through
compressor, comp1, to the unit called mixer, modeled by MIXE. Note that the flowsheet
of Fig. 6.14 shows two mixers to mix two feed streams and then two recycle streams, while
here the topology includes just one mixer for all four streams.

The liquid, Stream 8, from the flash is processed through three perfect-split
distillation columns, sep1, sep2, and sep3, all modeled by the black-box splitter CSEP. In
sep1, H2 and CH4 are vented as distillate Stream11; in sep2, benzene product, Stream 13,

SM-6-4
is removed as distillate; while in sep3, biphenyl is taken as a bottoms product, Stream 18,
and toluene is taken overhead as Stream 14, which is recycled to the mixer.

The two feeds to the process are 274.2 lbmol/h of pure toluene in Stream 1, and
makeup hydrogen (95% H2, 5% CH4) in Stream 2, which is subsequently adjusted by cont1,
as discussed above.

The process involves two recycle loops, which have three common streams: 15, 5,
and 6, any one of which could be selected as a single cut stream. Nevertheless, by default,
CHEMCAD selects two cut streams: 20, the hydrogen-rich recycle; and 14, the toluene
recycle. Therefore, initial guesses must be provided for Streams 20 and 14.

Referring to the topology table above, the equipment calculation sequence, by


default, is: 1 2 3 4 5 8 6 11 9 10. Other sequences are possible.

The overall material balance in millions of lb/yr, which is calculated from the molar
hourly flow rates by:

component flow rate, lbmol/h x MW x 8,410 h/yr,

is as follows:

Millions of pounds per year:


Component MW Toluene Makeup Gas Vent Benzene Biphenyl
feed gas purge
H2 2.016 10.09 5.47 0.04
CH4 16.043 4.23 38.76 2.37
Benzene 78.114 2.57 173.50
Toluene 92.141 212.48 0.44
Biphenyl 154.212 3.65
Total 212.48 14.32 47.24 2.41 173.50 3.65

From the table, it is seen that 173,500,000 lb/yr of benzene is produced from
212,480,000 lb/yr. This is a benzene yield of:

173.50
×100% = 96.3%
 78.114 
212.48 
 92.141 

The production of biphenyl by-product is 3,650,000 lb/yr, a relatively small


amount. However, the process is quite wasteful of hydrogen. The stoichiometric rate for
100% overall conversion of toluene to benzene is:
 2.016 
212.48  = 4.65 million lb/yr
 92.141 

SM-6-5
But, the makeup H2 is 10.09 million lb/yr, more than twice the stoichiometric amount.

Alternative 2:

The flowsheet in Fig. 6.14 is modified, as shown below in the new topology, by
eliminating the toluene column. Thus, toluene and biphenyl are not separated, but are
recycled together back to the mixer. This constitutes recycle of biphenyl to extinction. In
reac2, the equilibrium amount of biphenyl is produced. Upon convergence of the recycle
loops, the flow rate of biphenyl entering reac2 is exactly equal to the equilibrium amount
that leaves reac2. Therefore, no additional biphenyl is produced. The equilibrium amount
simply flows without change through the recycle loop.

Another modification is the replacement of the divider purge unit with membrane,
a CSEP model, to simulate a membrane separation. This requires another controller,
membn cont, using the CONT model. In membrane, where the first stream out is Stream
9 the purge, the split fraction of H2 is fixed at 0.1 so that 10% is purged in the retentate,
while 90% of the H2 is recycled in the permeate. An initial guess for the CH4 split fraction
is provided. This guess is adjusted by membn cont to achieve the specified hydrogen purity
in the permeate recycle of 95 mol% H2.

A further modification is the replacement of the single compressor unit, comp1,


which in Alternative 1 increases the recycle gas pressure from 500 to 570 psia, with a two-
stage system, including an intercooler that increases the permeate recycle gas pressure from
50 to 570 psia. The first compressor, comp1, discharges the gas at 170 psia and an elevated
temperature. The intercooler, cooler, reduces the gas temperature to 120oF before it enters
comp2, which provides the required pressure of 570 psia.

Equipment No. Equipment Model Equipment Name Stream Numbers


1 MIXE Mixer 1 2 17 16 -4
2 CONT H2 cont 4 -15
3 REAC reac1 15 -5
4 GIBS reac2 5 -6
5 FLAS flash 6 -7 -8
6 CSEP membrane 7 -9 -10
7 CONT membn cont 10 -19
8 CSEP sep1 8 -11 -12
9 CSEP sep2 12 -13 -17
11 COMP comp1 19 -20
12 HTXR cooler 20 -21
13 COMP comp2 21 -16

Again, convergence is achieved in just a few iterations to give the following overall
material balance in millions of lb/yr.

SM-6-6
Millions of pounds per year:
Component MW Toluene Makeup Gas Vent Benzene
feed gas purge
H2 2.016 6.84 2.17 0.05
CH4 16.043 2.87 38.63 1.05
Benzene 78.114 6.15 173.10
Toluene 92.141 212.48 1.04
Biphenyl 154.212
Total 212.48 9.71 47.99 1.10 173.10

These results show that the makeup gas flow rate is reduced considerably, by

 9.71 
1 −  × 100% = 32.2%
 14.32 

However, perhaps surprisingly, with elimination of the biphenyl by-product, the


benzene product rate is actually a little less (0.23% less), 173,100,000 lb/yr compared to
173,500,000 lb/yr for Alternative 1. This occurs because of the larger loss of benzene in
the retentate purge from the membrane separator.

Sizing of Membrane Separator:

From the simulator results, the material balance for the membrane unit is as follows:

Variable Feed Permeate Retentate


Pressure, psia 500 50 500
Flow rate,
lbmol/h
H2 1,283.0 1,154.7 128.3
CH4 347.0 60.7 286.3
Benzene 9.4 0.0 9.4
Toluene 1.3 0.0 1.3
Biphenyl 0.0 0.0 0.0
Total 1,640.7 1,215.4 425.3

For a gas permeation unit, the mass transfer equation for H2 is:

nH 2 = PM A∆pH 2 (1)

PM = permeance for hydrogen = 20 SCFH (60oF, 1 atm) of H2/ft2-100 psia Δp of H2


The H2 permeation rate = 1,154.7 lbmol/h. At 60oF and 1atm, 379 SCF = 1 lbmol.

SM-6-7
Therefore, the permeation rate = 1,154.7(379) = 437,600 SCFH.

1 1,283.0 128.3  
Average pH 2 on the feed-retentate side = 500 +   = 271 psia.
2 1,640.7 425.3  

 1,154.7 
On the permeate side, p H 2 = 50  = 47.5 psia. Therefore, Δ pH 2 = 271 - 47.5 = 223.5 psia
 1,215.4 

nH2 437,600
From Eq. (1), membrane area = A = = = 9,790 ft 2
PM ∆p H 2  223.5 
20 
 100 

If membrane modules containing 3,300 ft2, in units with 1-1/2-ft diameter by 8 ft long,
were available, three modules would be required.

SM-6-8
6.5 In the graph below, over the temperature range from 84 to 203°C, the rate constant
for the first reaction is the highest. Hence, the selectivity to species C is favored
over this temperature range.

2.10E-03

2.20E-03

2.30E-03

2.40E-03

2.50E-03

2.60E-03

2.70E-03

2.80E-03
0

-1
ln(k1)
-2 ln(k2)

-3 ln(k3)
ln(k4)
-4
ln(k)

-5

-6

-7

-8

-9

-10
1/T (K^-1)

SM-6-9
6.6 In one distribution of chemicals, as illustrated below, PM and HOAc are fed to the
reactive distillation above the trays containing acid-resin catalyst. PMA, the least
volatile species, concentrates in the bottoms product, along with unreacted PM and
HOAc. During process synthesis, it is reasonable to assume that the fractional
conversion of the reactants is comparable to that in a fixed-bed reactor. The lighter
water product concentrates in the distillate. The unreacted PM and HOAc distribute
in the distillate and bottoms product. This distribution can be assumed initially and
checked eventually by simulation. Note that for the fixed-bed reactor, kinetic data
were provided by ARCO (see the design report: Dunn, M.R., M. Feehery, and M.B.
Shook, PMA Manufacture by Fixed-bed and Reactive Distillation Processes, Dept.
of Chem. Eng., Univ. of Pennsylvania, 1993.)

H2O

PM
HOAc
Catalyst
Section

PMA

SM-6-10
6.7 ASPEN PLUS Flowsheet – simulation results can be reproduced using the
files EXER6-7A.bkp, EXER6-7B.bkp, EXER6-
7C.bkp, and EXER6-7D.bkp in the ASPEN folder,
under Computer Solution Files, associated with the
Solution Manual on the Wiley web site for this book.

R1
SFEED SOUT

RSTOIC

EVAPOR

R2
EFEED

REQUIL

ELIQ

ASPEN PLUS Program – for toluene hydrodealkylation reaction

IN-UNITS ENG
DEF-STREAMS CONVEN ALL
DESCRIPTION "General Simulation with English Units :
F, psi, lb/hr, lbmol/hr, Btu/hr, cuft/hr.
Property Method: None Flow basis for input: Mole
Stream report composition: Mole flow "
DATABANKS PURE10 / AQUEOUS / SOLIDS / INORGANIC / &
NOASPENPCD
PROP-SOURCES PURE10 / AQUEOUS / SOLIDS / INORGANIC
COMPONENTS
TOLUENE C7H8 TOLUENE /
HYDROGEN H2 HYDROGEN /
BENZENE C6H6 BENZENE /
METHANE CH4 METHANE
FLOWSHEET
BLOCK R1 IN=SFEED OUT=SOUT
BLOCK R2 IN=EFEED OUT=EVAPOR ELIQ
PROPERTIES RK-SOAVE
PROP-DATA RKSKIJ-1
IN-UNITS ENG
PROP-LIST RKSKIJ
BPVAL TOLUENE HYDROGEN .3900000000
BPVAL TOLUENE METHANE .0978000000
BPVAL HYDROGEN METHANE -.0222000000
BPVAL HYDROGEN TOLUENE .3900000000
BPVAL BENZENE METHANE .0209000000
STREAM EFEED
SUBSTREAM MIXED TEMP=1200. PRES=38.7 <atm>
MOLE-FLOW TOLUENE 100. / HYDROGEN 100.

SM-6-11
STREAM SFEED
SUBSTREAM MIXED TEMP=1200. PRES=38.7 <atm>
MOLE-FLOW TOLUENE 100. / HYDROGEN 100.

BLOCK R1 RSTOIC
PARAM PRES=38.7 <atm> DUTY=0.
STOIC 1 MIXED TOLUENE -1. / HYDROGEN -1. / BENZENE 1. &
/ METHANE 1.
CONV 1 MIXED TOLUENE 1.
BLOCK R2 REQUIL
PARAM NREAC=1 PRES=38.7 <atm> DUTY=0.
STOIC 1 TOLUENE -1. * / HYDROGEN -1. * / BENZENE 1. * &
/ METHANE 1. *
TAPP-SPEC 1 0.0

Tabulated Results

To (°F) P (atm) T100% (°F) TEquil (°F) ∆Hreac


(Btu/lbmol reactant)
C7H8 + H2 → C6H6 + CH4 1200 38.7 1512 1478* -21,460
SO2 + ½ O2 → SO3 77 1.0 2525 1331* -57,260
CO + ½ O2 → CO2 77 1.0 8646 5024 -121,700
C2H4Cl2 → C2H3Cl + HCl 932 26.0 -35.7 293.2 28,740

* These results may be inaccurate as the REQUIL subroutine reported


failure to close the mass balance.

SM-6-12
6.8 ASPEN PLUS Flowsheet – simulation results can be reproduced using the file
EXER6-8.bkp in the ASPEN folder, under Computer
Solution Files, associated with the Solution Manual on the
Wiley web site for this book.

R1
S1 S2

RSTOIC

Note that results computed using the REQUIL subroutine are identical to those
using the RSTOIC subroutine with the fractional conversion set at unity. Hence,
the fractional conversion at equilibrium is also unity over the temperature range
studied.

ASPEN PLUS Program

TITLE 'METHANOL REACTOR'


IN-UNITS ENG
DEF-STREAMS CONVEN ALL
DATABANKS PURE93 / AQUEOUS / SOLIDS / INORGANIC / &
NOASPENPCD
PROP-SOURCES PURE93 / AQUEOUS / SOLIDS / INORGANIC
COMPONENTS
CO CO CO /
H2 H2 H2 /
CH3OH CH4O CH3OH
FLOWSHEET
BLOCK R1 IN=S1 OUT=S2
PROPERTIES PSRK
STREAM S1
IN-UNITS MET
SUBSTREAM MIXED TEMP=25 <C> PRES=1.0
MOLE-FLOW CO 1.0 <lbmol/hr> / H2 10.0 <lbmol/hr> / CH3OH &
0 <lbmol/hr>
BLOCK R1 RSTOIC
IN-UNITS MET
PARAM PRES=1.0 DUTY=0
STOIC 1 MIXED CO -1 / H2 -2 / CH3OH 1
CONV 1 MIXED CO 1.0
SENSITIVITY S-1
DEFINE TEMP STREAM-VAR STREAM=S2 SUBSTREAM=MIXED &
VARIABLE=TEMP
TABULATE 1 "TEMP"
VARY MOLE-FLOW STREAM=S1 SUBSTREAM=MIXED COMPONENT=H2
RANGE LOWER="0" UPPER="40" INCR="1"
STREAM-REPOR MOLEFLOW MOLEFRAC

SM-6-13
Results

2500 Sensitiv ity S-1 Results Summary

TEMP
2000
1500
F
1000
500

0 2.5 5 7.5 10 12.5 15 17.5 20 22.5 25 27.5 30 32.5 35 37.5 40


VARY 1 S1 MIXED H2 MOLEF LOW LBMOL/HR

SM-6-14
6.9 ASPEN PLUS Flowsheet – simulation results can be reproduced using the file
EXER6-9.bkp in the ASPEN folder, under Computer
Solution Files, associated with the Solution Manual on the
Wiley web site for this book.

R1
S1 S2

RSTOIC

ASPEN PLUS Program

TITLE 'METHANOL REACTOR'


IN-UNITS ENG
DEF-STREAMS CONVEN ALL
DATABANKS PURE93 / AQUEOUS / SOLIDS / INORGANIC / &
NOASPENPCD
PROP-SOURCES PURE93 / AQUEOUS / SOLIDS / INORGANIC
COMPONENTS
CO CO CO /
H2 H2 H2 /
CH3OH CH4O CH3OH /
C12H26 C12H26 C12H26
FLOWSHEET
BLOCK R1 IN=S1 OUT=S2
PROPERTIES PSRK
STREAM S1
IN-UNITS MET
SUBSTREAM MIXED TEMP=25 <C> PRES=1.0
MOLE-FLOW CO 1.0 <lbmol/hr> / H2 2.0 <lbmol/hr> / CH3OH &
0 <lbmol/hr> / C12H26 5.0 <lbmol/hr>
BLOCK R1 RSTOIC
IN-UNITS MET
PARAM PRES=1.0 DUTY=0
STOIC 1 MIXED CO -1 / H2 -2 / CH3OH 1
CONV 1 MIXED CO 1.0
SENSITIVITY S-1
DEFINE TEMP STREAM-VAR STREAM=S2 SUBSTREAM=MIXED &
VARIABLE=TEMP
TABULATE 1 "TEMP"
VARY MOLE-FLOW STREAM=S1 SUBSTREAM=MIXED COMPONENT=C12H26
RANGE LOWER="0" UPPER="25" INCR="1"
STREAM-REPOR MOLEFLOW MOLEFRAC

SM-6-15
Results
2500

Sensitivity S-1 Results Summary

TEMP
2000
1500
F
1000
500

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25
VARY 1 S1 MIXED C12H26 M OLEFLOW LBMOL/HR

SM-6-16
6.10 ASPEN PLUS Flowsheet – simulation results can be reproduced using the file
EXER6-10.bkp in the ASPEN folder, under Computer
Solution Files, associated with the Solution Manual on the
Wiley web site for this book.

H2-FEED

H2-1 H2-5
S1
H2-2 H2-4
SEP

H2-3

R1 R2 R3 R4 R5
CO-FEED P1 P2 P3 P4 PROD
RSTOIC RSTOIC RSTOIC RSTOIC RSTOIC

Stream Variables – Hydrogen Temperature = -25°C

CO-FEED H2-1 H2-2 H2-3 H2-4


---------------------------

STREAM ID CO-FEED H2-1 H2-2 H2-3 H2-4


FROM : ---- S1 S1 S1 S1
TO : R1 R1 R2 R3 R4

SUBSTREAM: MIXED
PHASE: VAPOR VAPOR VAPOR VAPOR VAPOR
COMPONENTS: KMOL/HR
HYDROGEN 0.0 0.1814 0.1814 0.1814 0.1814
CARBO-01 0.4535 0.0 0.0 0.0 0.0
METHA-01 0.0 0.0 0.0 0.0 0.0
TOTAL FLOW:
KMOL/HR 0.4535 0.1814 0.1814 0.1814 0.1814
KG/HR 12.7053 0.3657 0.3657 0.3657 0.3657
L/MIN 184.9658 61.6162 61.6162 61.6162 61.6162
STATE VARIABLES:
TEMP K 298.1500 248.1500 248.1500 248.1500 248.1500
PRES ATM 1.0000 1.0000 1.0000 1.0000 1.0000
VFRAC 1.0000 1.0000 1.0000 1.0000 1.0000
LFRAC 0.0 0.0 0.0 0.0 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
CAL/MOL -2.6401+04 -341.4515 -341.4515 -341.4515 -341.4515
CAL/GM -942.5524 -169.3808 -169.3808 -169.3808 -169.3808
CAL/SEC -3326.5042 -17.2088 -17.2088 -17.2088 -17.2088
ENTROPY:
CAL/MOL-K 21.3194 -1.2546 -1.2546 -1.2546 -1.2546
CAL/GM-K 0.7611 -0.6223 -0.6223 -0.6223 -0.6223
DENSITY:
MOL/CC 4.0872-05 4.9077-05 4.9077-05 4.9077-05 4.9077-05

SM-6-17
GM/CC 1.1448-03 9.8934-05 9.8934-05 9.8934-05 9.8934-05
AVG MW 28.0104 2.0158 2.0158 2.0158 2.0158

H2-5 H2-FEED P1 P2 P3
---------------------

STREAM ID H2-5 H2-FEED P1 P2 P3


FROM : S1 ---- R1 R2 R3
TO : R5 S1 R2 R3 R4

SUBSTREAM: MIXED
PHASE: VAPOR VAPOR VAPOR VAPOR VAPOR
COMPONENTS: KMOL/HR
HYDROGEN 0.1814 0.9071 0.0 0.0 0.0
CARBO-01 0.0 0.0 0.3628 0.2721 0.1814
METHA-01 0.0 0.0 9.0718-02 0.1814 0.2721
TOTAL FLOW:
KMOL/HR 0.1814 0.9071 0.4535 0.4535 0.4535
KG/HR 0.3657 1.8287 13.0710 13.4368 13.8025
L/MIN 61.6162 308.0811 482.3209 649.3317 751.8607
STATE VARIABLES:
TEMP K 248.1500 248.1500 777.1635 1046.2703 1211.4917
PRES ATM 1.0000 1.0000 1.0000 1.0000 1.0000
VFRAC 1.0000 1.0000 1.0000 1.0000 1.0000
LFRAC 0.0 0.0 0.0 0.0 0.0
SFRAC 0.0 0.0 0.0 0.0 0.0
ENTHALPY:
CAL/MOL -341.4515 -341.4515 -2.6538+04 -2.6674+04 -2.6811+04
CAL/GM -169.3808 -169.3808 -920.9175 -900.4604 -881.0875
CAL/SEC -17.2088 -86.0443 -3343.7131 -3360.9220 -3378.1308
ENTROPY:
CAL/MOL-K -1.2546 -1.2546 20.0604 15.0950 9.1885
CAL/GM-K -0.6223 -0.6223 0.6961 0.5095 0.3019
DENSITY:
MOL/CC 4.9077-05 4.9077-05 1.5674-05 1.1643-05 1.0055-05
GM/CC 9.8934-05 9.8934-05 4.5167-04 3.4489-04 3.0596-04
AVG MW 2.0158 2.0158 28.8167 29.6231 30.4294

P4 PROD
-------

STREAM ID P4 PROD
FROM : R4 R5
TO : R5 ----

SUBSTREAM: MIXED
PHASE: VAPOR VAPOR
COMPONENTS: KMOL/HR
HYDROGEN 0.0 0.0
CARBO-01 9.0718-02 0.0
METHA-01 0.3628 0.4535
TOTAL FLOW:
KMOL/HR 0.4535 0.4535
KG/HR 14.1683 14.5340
L/MIN 820.9443 870.6021
STATE VARIABLES:
TEMP K 1322.8387 1402.9065
PRES ATM 1.0000 1.0000
VFRAC 1.0000 1.0000
LFRAC 0.0 0.0
SFRAC 0.0 0.0
ENTHALPY:
CAL/MOL -2.6948+04 -2.7084+04

SM-6-18
CAL/GM -862.7148 -845.2668
CAL/SEC -3395.3397 -3412.5486
ENTROPY:
CAL/MOL-K 2.7157 -4.5163
CAL/GM-K 8.6944-02 -0.1409
DENSITY:
MOL/CC 9.2088-06 8.6835-06
GM/CC 2.8764-04 2.7824-04
AVG MW 31.2358 32.0421

Product Temperature as Function of Hydrogen Temperature

Sensitiv ity S-1 Results Summary


1435

TEMP
1430
1425
1420
K
1415
1410
1405

240 245 250 255 260 265 270 275 280 285 290 295 300
VARY 1 HFEED MIXED TEMPERAT URE K

Adiabatic reaction temperature (from Exer. 6.8) = 2,116°F = 1,431 K

Clearly, the cold shots of hydrogen over the temperature range above do not
significantly reduce the maximum temperature in the flowsheet.

SM-6-19
6.11 ASPEN PLUS Flowsheet – simulation results can be reproduced using the file
EXER6-11.bkp in the ASPEN folder, under Computer
Solution Files, associated with the Solution Manual on the
Wiley web site for this book.

R1 H1 R2 H2
1 2 3 4

RSTOIC HEATER RSTOIC HEATER

R4 H3 R3
8 7 6

RSTOIC HEATER RSTOIC

ASPEN PLUS Program

IN-UNITS ENG
DEF-STREAMS CONVEN ALL
DATABANKS PURE10 / AQUEOUS / SOLIDS / INORGANIC / &
NOASPENPCD
PROP-SOURCES PURE10 / AQUEOUS / SOLIDS / INORGANIC
COMPONENTS
CO CO CO /
H2 H2 H2 /
METHANOL CH4O METHANOL
FLOWSHEET
BLOCK R1 IN=1 OUT=2
BLOCK H1 IN=2 OUT=3
BLOCK R2 IN=3 OUT=4
BLOCK H2 IN=4 OUT=5
BLOCK R3 IN=5 OUT=6
BLOCK H3 IN=6 OUT=7
BLOCK R4 IN=7 OUT=8
PROPERTIES PSRK
STREAM 1
SUBSTREAM MIXED TEMP=25. <C> PRES=1. <atm> MOLE-FLOW=3.
MOLE-FLOW CO 1. / H2 2.
BLOCK H1 HEATER
PARAM TEMP=77. PRES=1. <atm>
BLOCK H2 HEATER
PARAM TEMP=77. PRES=1. <atm>
BLOCK H3 HEATER
PARAM TEMP=77. PRES=1. <atm>
BLOCK R1 RSTOIC
PARAM PRES=1. <atm> DUTY=0.
STOIC 1 MIXED H2 -2. / CO -1. / METHANOL 1.
CONV 1 MIXED CO 0.1
BLOCK R2 RSTOIC
PARAM PRES=1. <atm> DUTY=0.
STOIC 1 MIXED CO -1. / H2 -2. / METHANOL 1.
CONV 1 MIXED CO 0.1

SM-6-20
BLOCK R3 RSTOIC
PARAM PRES=1. <atm> DUTY=0.
STOIC 1 MIXED CO -1. / H2 -2. / METHANOL 1.
CONV 1 MIXED CO 0.1
BLOCK R4 RSTOIC
PARAM PRES=1. <atm> DUTY=0.
STOIC 1 MIXED CO -1. / H2 -2. / METHANOL 1.
CONV 1 MIXED CO 0.1
DESIGN-SPEC DS-1
DEFINE T1 STREAM-VAR STREAM=2 SUBSTREAM=MIXED VARIABLE=TEMP
SPEC "T1" TO "572"
TOL-SPEC "0.01"
VARY BLOCK-VAR BLOCK=R1 VARIABLE=CONV SENTENCE=CONV ID1=1
LIMITS "0" "1"
DESIGN-SPEC DS-2
DEFINE T2 STREAM-VAR STREAM=4 SUBSTREAM=MIXED VARIABLE=TEMP
SPEC "T2" TO "572"
TOL-SPEC "0.01"
VARY BLOCK-VAR BLOCK=R2 VARIABLE=CONV SENTENCE=CONV ID1=1
LIMITS "0" "1"
DESIGN-SPEC DS-3
DEFINE T3 STREAM-VAR STREAM=6 SUBSTREAM=MIXED VARIABLE=TEMP
SPEC "T3" TO "572"
TOL-SPEC "0.01"
VARY BLOCK-VAR BLOCK=R3 VARIABLE=CONV SENTENCE=CONV ID1=1
LIMITS "0" "1"
DESIGN-SPEC DS-4
DEFINE T4 STREAM-VAR STREAM=8 SUBSTREAM=MIXED VARIABLE=TEMP
SPEC "T4" TO "572"
TOL-SPEC "0.01"
VARY BLOCK-VAR BLOCK=R4 VARIABLE=CONV SENTENCE=CONV ID1=1
LIMITS "0" "1"

Stream Variables

1 2 3 4 5
---------

STREAM ID 1 2 3 4 5
FROM : ---- R1 H1 R2 H2
TO : R1 H1 R2 H2 R3

SUBSTREAM: MIXED
PHASE: VAPOR VAPOR VAPOR VAPOR MIXED
COMPONENTS: LBMOL/HR
CO 1.0000 0.7571 0.7571 0.5365 0.5365
H2 2.0000 1.5142 1.5142 1.0730 1.0730
METHANOL 0.0 0.2428 0.2428 0.4634 0.4634
TOTAL FLOW:
LBMOL/HR 3.0000 2.5142 2.5142 2.0730 2.0730
LB/HR 32.0421 32.0421 32.0421 32.0421 32.0421
CUFT/HR 1176.9648 1895.4433 985.4270 1562.5582 756.6789
STATE VARIABLES:
TEMP F 77.0000 571.9999 77.0000 571.9999 77.0000
PRES PSI 14.6959 14.6959 14.6959 14.6959 14.6959
VFRAC 1.0000 1.0000 1.0000 1.0000 0.9320
LFRAC 0.0 0.0 0.0 0.0 6.7969-02
SFRAC 0.0 0.0 0.0 0.0 0.0

SM-6-21
ENTHALPY:
BTU/LBMOL -1.5840+04 -1.8900+04 -2.2657+04 -2.7479+04 -3.2747+04
BTU/LB -1483.0187 -1483.0187 -1777.8796 -1777.8796 -2118.7000
BTU/HR -4.7519+04 -4.7519+04 -5.6967+04 -5.6967+04 -6.7888+04
ENTROPY:
BTU/LBMOL-R 8.3703 10.1384 5.1997 6.0491 -1.4520
BTU/LB-R 0.7836 0.7955 0.4080 0.3913 -9.3947-02
DENSITY:
LBMOL/CUFT 2.5489-03 1.3265-03 2.5515-03 1.3267-03 2.7397-03
LB/CUFT 2.7224-02 1.6905-02 3.2516-02 2.0506-02 4.2346-02
AVG MW 10.6807 12.7440 12.7440 15.4562 15.4562

6 7 8
-----

STREAM ID 6 7 8
FROM : R3 H3 R4
TO : H3 R4 ----

SUBSTREAM: MIXED
PHASE: VAPOR MIXED VAPOR
COMPONENTS: LBMOL/HR
CO 0.2816 0.2816 0.0
H2 0.5632 0.5632 0.0
METHANOL 0.7183 0.7183 1.0000
TOTAL FLOW:
LBMOL/HR 1.5632 1.5632 1.0000
LB/HR 32.0421 32.0421 32.0421
CUFT/HR 1177.5678 397.5299 506.2992
STATE VARIABLES:
TEMP F 572.0021 77.0000 241.6702
PRES PSI 14.6959 14.6959 14.6959
VFRAC 1.0000 0.6486 1.0000
LFRAC 0.0 0.3513 0.0
SFRAC 0.0 0.0 0.0
ENTHALPY:
BTU/LBMOL -4.3428+04 -5.4104+04 -8.4578+04
BTU/LB -2118.7000 -2639.5875 -2639.5875
BTU/HR -6.7888+04 -8.4578+04 -8.4578+04
ENTROPY:
BTU/LBMOL-R -2.0271 -18.7422 -27.9730
BTU/LB-R -9.8897-02 -0.9143 -0.8730
DENSITY:
LBMOL/CUFT 1.3275-03 3.9324-03 1.9751-03
LB/CUFT 2.7210-02 8.0603-02 6.3287-02
AVG MW 20.4972 20.4972 32.0421

Selected Process Unit Output

BLOCK: R1 MODEL: RSTOIC


------------------------------
INLET STREAM: 1
OUTLET STREAM: 2
PROPERTY OPTION SET: PSRK RKS-MHV1 EQUATION OF STATE

SM-6-22
*** MASS AND ENERGY BALANCE ***
IN OUT GENERATION RELATIVE DIFF.
TOTAL BALANCE
MOLE(LBMOL/HR) 3.00000 2.51428 -0.485723 -0.185037E-16
MASS(LB/HR ) 32.0422 32.0422 -0.221752E-15
ENTHALPY(BTU/HR ) -47519.1 -47519.1 0.153116E-15

*** INPUT DATA ***

SIMULTANEOUS REACTIONS
STOICHIOMETRY MATRIX:

REACTION # 1:
SUBSTREAM MIXED :
CO -1.00 H2 -2.00 METHANOL 1.00

REACTION CONVERSION SPECS: NUMBER= 1


REACTION # 1:
SUBSTREAM:MIXED KEY COMP:CO CONV FRAC: 0.2429

TWO PHASE PQ FLASH


SPECIFIED PRESSURE PSI 14.6959
SPECIFIED HEAT DUTY BTU/HR 0.0
MAXIMUM NO. ITERATIONS 30
CONVERGENCE TOLERANCE 0.00010000

*** RESULTS ***


OUTLET TEMPERATURE F 572.00
OUTLET PRESSURE PSI 14.696
VAPOR FRACTION 1.0000

REACTION EXTENTS:

REACTION REACTION
NUMBER EXTENT
LBMOL/HR
1 0.24286

V-L PHASE EQUILIBRIUM :

COMP F(I) X(I) Y(I) K(I)


CO 0.30114 0.30114 0.30114 902.20
H2 0.60227 0.60227 0.60227 1091.1
METHANOL 0.96593E-01 0.96593E-01 0.96593E-01 11.301

SM-6-23
6.12 First, establish the phase conditions for entering toluene at 70oF and 20 psia (typical
of storage conditions) and exiting toluene at 450oF and 75 psia. Because the stream
is a pure component, the phase conditions can be established from the vapor
pressure curve for toluene, show schematically below, which has a normal boiling
point of 231oF and critical point at 606oF and 100 psia. As seen, toluene enters as
a subcooled liquid and exits as a superheated vapor.

SM-6-24
Process Synthesis:

Three possible processes are shown below. In Process 1, the toluene is vaporized
in a heat exchanger. The vapor is then compressed to the desired pressure level. Enough
superheat is provided in the heat exchanger to enable the vapor to reach the desired
temperature level in the compressor.

In Process 2, the toluene pressure is raised to the desired level as a liquid in a pump.
The liquid is then heated, vaporized, and superheated in the heat exchanger. Process 3 is a
variation of Process 2. Three heat exchangers replace the single unit in Process 2. The
first heat exchanger heats the liquid to the boiling point at the elevated pressure. The
second heat exchanger vaporizes the liquid isothermally. The third exchanger provides the
superheat to the vapor.

SM-6-25
Process Analysis:

Typical results for the simulation of the three processes with CHEMCAD are
shown below. The flow through each heat exchanger is accompanied by a 5 psi pressure
drop. Note the very low Hp of the liquid pump in Processes 1 and 2, compared to the more
than 100 times Hp of the gas compressor in Process 1. This is due to the much lower
density of the vapor compared to the liquid. This much lower Hp is offset somewhat by
the almost 15% higher heat exchange duty of Processes 2 and 3 compared to Process 1.

Recommendation:

In general, as shown in this exercise, it is much less expensive to pressurize the liquid phase
rather than the gas phase. Purchase and operating costs for pumps are much lower than
corresponding costs for gas compressors. Using methods presented later in this textbook,
the comparison for Process 1 and Processes 2 and 3 is as follows:

Process 1 Processes 2 and 3


Gas compressor Liquid pump
Purchase cost (1990) $ 70,000 $ 1,400
Annual utility cost $60,000 $ 500
at $0.07/kw-hr

Process 2 or 3 is preferred. Process 3 is more expensive, but it is easier to design and


operate.

SM-6-26

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