F.V.O.

Nr:

2693

Technische Universiteit Delft

Vakgroep Chemische Technologie

Verslag behorende
bij het fabrieksvoorontwerp
van

A.H. Amer
R.F. de Ruiter

onderwerp:

The production of methyl ethyl ketone

from n-butene

adres:

Dr. H. Colijnlaan 187

A.M. de yonglaan 27

2283 XG Rijswijk

3221 VA Hellevoetsluis

opdrachtdatum:

20-10-1986

verslagdatum:

12-07-1988

Contents
page
Abstract

Conclusions and reco endations

General introduction

1.1
1.2
1.3
1.4
1.5
1.6
1.7

Uses and product ion

Manufacture
Choice of process
Plant capacity
Health and safety
Feedstock
Process description

3
4
5
6
6
6
7

Secondary butyl alcohol product ion

2.1
2.1. 1
2.1. 2
2.1. 3
2.1. 4
2.1. 5
2.1. 6
2.2
2.2.1
2.2.2
2.3
2.4
2.5
2.5.1
2.5.2
2.6
2.6.1
2.6.2

Butene absorber
Liquification
Absorption kinetics
Material balance
Heat balance and cooling
Design
Gas-liquid separator
Hydrolysis tank
Material balance and design
Heat balance
SBA stripper
Caustic scrubber
Sulfuric acid reconcentration unit
Reconcentration processes
Drum design
SBA purification unit
Liquid-liquid separator
Azeotropic distillation unit

9
9
9
10
10

Methyl ethyl ketone product ion

27

3.1
3.1.1
3.1. 2
3.1. 3
3.1. 4
3.1. 5
3.1. 6
3.2

27
27
28

3.3

Dehydrogenation reactor
Convers ion of SBA
Reaction thermodynamics
Catalyst choice
Kinetics of a Cu/Ni-catalyst
Pressure influences
Design
Hydrogen recovery
MEK purification unit

Mass and heat balance, strea. data

39

Apparatus specifications

52

Cost esti.ation and econo.ics

67

References

73

12
13
14
14
15
16
20

21
21
22
23
23
24

29
30

33

34
35
35

....

__ ._--

_._- -- -- - --

- - - -- - - --

Abstract

In

this

preliminary

design

the

production

of

methyl ethyl

ketone (MEK) from normal butene, with secondary butyl alcohol (SBA)
as intermediate, is described. This design is split into two parts.
In the first part SBA is obtained from n-butene by absorption in
sulfuric acid, followed by hydrolysis with water. Sulfurie acid and
SBA

are

separated

in

stripper.

The

sulfurie

acid

is

reconcentrated and recycled to the absorber. The SBA is purified in

an azeotropic distillation unit, using diisobutylene as entrainer.
In
mul ti

the second part of the design, SBA is vaporized and fed to a

t ubular,

isothermi c

reactor,

fi lIed

wi th a Cu/Ni on S iO Zo

catalyst.

The SBA is dehydrogenized, forming MEK and hydrogene The

hydrogen

is purified and sold as a valuable by-product. The MEK is

purified in two fractionation columns and obtained with a purity of

99.1 wt"-%.
The
economie

capacity

of

evaluation

the

plant is 33,731 tons of MEK per year. An

shows

that

this

within approximately 1.5 to 2 years.

plant

can pay itself back

Conclusions and reco endations

The

extractive

separated
for

unit,

where

SBA

and

water are

is simulated, using the UNIFAC group contribution method

predicting

used

distillation

as

an

haviour

activity cofficints. This simulation can only be

indication. To make an accurate prediction of the be-

of

this

thermodynamic

unit,

it

is

necessary

to

have

reliable

data. The same problem occurs with the SBA stripper.

The influence of sulfuric acid on the equilibrium data could not be

forecasted and the assumptions made are rat her rigourous.
Although

can

be

the

equipment

obtained

equipment

is attached, it is likely that n-butene

in liquified state. The compressor covers 17% of

and

costs

costs

investment,
the

compressor

form

this

because

the

base

percentage

in the used economic model the

for

obtaining the total capital

has great effect on the economics of

proces. Nevertheless a pay-out time of 1.5 years and an inter-

Dal rate of return of 58.2% give a good indication for the expected
perspectives.
costs

and

MEK

This

is

selling

due to the great difference between butene

prices. The price difference of f.200,-/t

between SBA and MEK can not justify the design of an SBA convers ion
plant only.

General introduction

1.1

Uses and production

Methyl

ethyl ketone is one of the lowest priced solvents in its

boiling range and it is widely used as a solvent in a great variety

of

coating systems. As a solvent for lacquers, MEK is particularly

advantageous

because

it

provides low viscosity solutions at high

solid

contents without affecting film properties. MEK is also used

as

dewaxing

solvent

for

agent in the refining of lubricating oils and as a

adhesives, rubber, cement, printing inks and cleaning

solutions.

It is used in vegetable-oil extract ion processes and in

azeotropic

separation schemes in refineries [IJ. Furthermore it is

used

in

the pharmaceutical industry. Table(l-l)lists the main uses

of MEK for 1977 in the USA.

Table(l-l): Methyl ethyl ketone uses

Use

Percentage

Vinyl coatings

34

Nitrocellulose coatings

14

Adhesives

14

Acrylic coatings

12

7
7

Miscellaneous coatings
Lube-oil dewaxing
Miscellaneous and export

12

The output of MEK in the United States of America reached 27,000

tons

per

nually

by

year
6

in 1976 and the demand is expected to increase an%. The situation is similar in Western Europe and in

Japan. The total annual production of MEK in Western Europe in 1976

was 220,000 tons.
The
solvents

industrial
such

In Japan it was 65,100 tons.

importance

of MEK is rising because the use of

as alkyl aromatics and branched ketones, which have

high

biostability

tion

of

the

will become restricted for reasons of conserva-

environment, and they can be replaced by MEK.

In the

USA this is already alegal requirement [2J.

1.2

Manufacture

Methyl ethyl ketone can be manufactured by a direct oxidation of

n-butenes

in

aqueous

solutions of palladium and cupric chlorides

[3 J :

+
It

----)

is also commercially available as a byproduct from liquid-phase

oxidation of butane to acetic acid.

In general MEK is produced by a two-step process from n-butenes.
The

first

butanol

step

(SBA).

is

the

convers ion

of

n-butenes into secondary

In the second step the formed SBA is converted into

MEK, wether by oxidation or by dehydrogenation.

Secondary
in

the

butanol

vapor

phase

containing

phosphoric

Fe,

temperature

at

can be produced by the hydration of l-butene

by

passage with steam over asolid catalyst

acid and the oxides of metals as Zn, Mg and

of 240C and a pressure of 9.9 atm. [4], or

over a mixture of boric acid and phosphoric acid catalysts at 388C

and 380 atm., with a maximum convers ion of 8.5 % per pass [5J:
+

-----)

About 10 percent of the reacted butene is lost by polymerisation.

Secondary butanol is usually produced by absorption of n-butenes
in sulfurie acid, followed by hydrolysis with water:
-----)
(-----

CH 3 -H-C&H s
OS03 H
The

+ 3 H&O

CH 3 -H-C&H s + 2 H&O
OS03 H

-----)

absorption of but ene can be carried out in 65 wt-% sulfurie

acid

at

50-60 o C,

in 75-80 wt-% acid at 30-50 o C and in 90-100 wt-%

acid

at

15C

or below [4]. Gaseous butenes can be absorbed in 80

wt-%

acid

at

a temperature of 43C and atmospheric pressure [6J,

liquid

butenes

can

be

absorbed

at

a temperature of 38C and a

pressure of 2-3 atm.(7].

The

second

butanol
done

to

in

phase

is

dehydrogenation or oxidation of secondary

methyl ethyl ketone. The dehydrogenation of SBA can be

the

catalysts

step
liquid

phase

at

temperature

of l50-250oC with

as raney nickel or copper chromite (8], and in the vapor

over copper or zinc catalysts at higher temperatures and low

pressures.

The oxidation is done by air over copper or zinc oxides

at temperatures between 250 and 400C.

Several

other

licenced methods for producing MEK are described

in literature (1]:
-Oxidation

by

acid

dichromate,

alkaline

permanganate, hydrogen

peroxide or sodium perchlorate.

-Free radical addition of acetaldehyde and ethylene:
free radical initiator
-----------------------)
-Isomerization of butene oxide:

-Isomerization of isobutyraldehyde:

1.3
Most
from

Choice of process
of

the methyl ethyl ketone now being produced is obtained

n-butenes

in

butenes

to

of

alcohol

the

energy
timated,

two

stages:

the sulfuric acid hydration of n-

produce secondary butanol, followed by dehydrogenation

to ketone. Although sulfurie acid hydration is an

consuming process and corrosion aspects can not be underesits

technology

has been proven for decennia and, when a

hydration

plant

is

combined

with a refinery or a naphta cracker

(what are also favorable combinations regarding the butene supply),

a major part of the required energy can be supplied from waste-heat
from

flue

gases.

preferabie
easier,

to

the

In

the
MEK

the

second

oxidation,
yield

is

stage

as

the

higher

the

dehydrogenation is

temperature regulation is

and

hydrogen

is

formed

as

byproduct.
1.4

Plant capacity

A design had to be made for a plant, capable to produce at least

30,000 ton MEK per year. To reach this target the feed of the plant
must be 23,347 tons per year of n-butenes (at a MEK yield of 100%).
The plant is designed to run continuous for 300 days per year
hours

per

actual

MEK

purity

of

year).

The

actual

production
99.13

(7~

butene feed is 26,457 t/yr and the

is 33,731 t/yr. The MEK is obtained with a

wt-%

and the overall MEK yield from n-butene is

98.35%.
1.5
The
the

Health and safety

toxic

weight of methyl ethyl ketone in air is 200 ppm. For

intermediate

SBA

this

is

150

ppm. MEK is highly flammable

(flashpoint -lOC) and should be used with caution. The lower explosion limit is 1.8 vol-% in air and the upper explosion limit is 9.5
vol-%

in

air.

For n-butene these limits are respectivily 1.6 and

9.7 vol-% in air and for SBA 1.7 and 9.8 vol-% in air. The electrical conductivity of MEK has a value of 2*10 7 pS/m, which means that
there is no danger for static charge build-up. Care should be taken
when

MEK

is

stored

for

longer periods. Storage in carbon steel

tanks will lead to peroxide formation. Special alloys are available

which do not initiate this reaction.
1.6

Feedstock

Butylene
methylpropene
butene.
These

The
four

is
or

the

name

of

mixture

of

four

isomers:

2-

isobutylene, l-butene, cis-2-butene and trans-2-

last
isomers

three

are referred to as normal- or n-butenes.

and

butane are treated as a C4 -group because

6

7,
j

they

are

of ten

obtained

as

mixture

from

cracked petroleum

fractions.
For

the

mediate

for

necessary
In

manufacture of secondary butyl alcohol (SBA) as interthe

product ion

of

methyl

ethyl ketone (MEK) it is

to have a feedstock in which the isobutylene is removed.

electrophilic

times

faster

would

lead

reactions

than

the

isobutylene will react about thousand

n-butenes and in our reaction scheme this

to

formation of tertiary butyl alcohol. However, this

difference

in

reactivity

isobutylene

from

extraction

can

can

also

be

used

to

separate

the

the n-butenes. For this separation sulfuric acid

be used.

Isobutylene can quantitativily be removed

in a solution of 45-60% HzSO. at 30C.

Butane

in

absorption
scheme

the

does

not

have affect on the but ene

because it does not react with sulfuric acid. As in our

unreacted

would

feedstock

lead

to

butenes

are

accumulation

recycled,
and

to

inerts in the feedstock

prevent this, a part of the

recycle stream must be purged (e.g. to a furnace).

We

assumed

to

have

a gaseous feedstock at 1 atmosphere which

only containes n-butenes in their ~a~~~~l ~q~i]~b~~u~ distribution

at 300 K:
2 % l-butene, 9 % cis-2-butene and 89 % trans-2-butene
[24].
1.7

Process description

Gaseous
ture

of

butenes
25C

with a pressure of 1 atmosphere and a tempera-

are charged to a compressor, which is followed by a

cooler, where liquification takes place at a pressure of 3 atm.

The

liquified

charged
to

to

form

butenes are mixed with 80 wt-% sulfuric acid and

an absorption column. The acid reacts with the butenes

butyl

sulfates and deprotonated secondary butyl alcohol.

The reaction is exothermic, and heat is withdrawn by cooling.

The

conversion

of

butenes

is

practically complete (> 98 %).

Af ter the absorption stage the pressure is decreased to atmospheric

and

residual

separator
hydrolyzer,

butenes

and

are

where

are

removed

recycled.
water

is

from

the

product in a phase

The acid-sulfate mixture flows to a

added and secondary butyl alcohol is

formed.
The hydrolyzate is fed to a column where the alcohol is stripped
from

the

diluted

acid

by means of life steam. Entrained acid is

r.;

captured
vapor

in

demister

and

traces of acid in the alcohol-water

are removed in a scrubber with diluted sodium hydroxide. The

scrubbed vapors are then condensed to form a crude containing water

and alcohol.
The diluted acid is reconcentrated in two stages and is recycled
to the absorption column.
The

crude

alcohol

is,

af ter separation in two liquid phases,

purified in a fractionation column. Diisobutylene (2,4,4-trimethyll-pentene)

boiling
is

is added to the column as an entrainer to form a light-

ternary

withdrawn

azeotrope in the top of the column, while alcohol

in the bottom.

In a second column water is withdrawn

from the remaining mixture.

The
to

secondary butyl alcohol is vaporized, preheated and charged

a tubular reactor where dehydrogenation to MEK takes place. The

tubes are packed with a Cu/Ni on SiO z catalyst and are direct-fired
to

maintain

contains
water

areaction temperature of 310C. The reactor effluent

MEK,

(the

column).

unconverted alcohol, hydrogen and a small amount of

water

This

separator

comes

effluent

where

the

with
is

the alcohol from the fractionation

condensed

hydrogen

and

charged

to

a phase

is removed. The flue gasses of the

furnace are used for reconcentrating the diluted sulfuric acid.

The
columns.
and

percent.

methyl
In
trace
The

ethyl

ketone

is

purified

in

two

fractionation

the top of the first column a mixture of MEK, alcohol

of

water

bottom

is withdrawn with a purity of MEK of 98.9

product is charged to the second column. The

top product of the second column contains MEK with a purity of 99.3
percent and the bottom product contains the remaining alcohol which
is recycled to the reactor.

Secondary butyl alcohol product ion

2.1

Butene absorber

2.1. 1

Liquification

The liquification pressure of the mixture of butenes

2-butene,

trans-

(89~

cis-2-butene, 2% l-butene) is calculated by using the

9~

Antoine equation for the vapor pressure:

(1)

where
A,

p is the pressure in mm Hg and T is the temperature in K and

Band

Care to the vapor related constants. Values for these

constants are mentioned in appendix

the

vapor

A-I . At a temperature of 25C

pressure of the butene mixture becomes 1953 mm Hg (2.57

atm). The operating pressure in the column is fixed at 3 atm.

The

gaseous

temperature
liquified

mixture of n-butenes at atmospheric pressure and a

of

25C

co~

compressed

to 3 atm in a compressor and

The outlet temperature of the compressor is

.
.-XH.\'
(
l'
.
the actual ~ of the compressor 1S
73.72 kW. The condenser

71C,

in a

is

duty

is

1.76 MM kJ/hr (489 kW). These calculations have been done

with

the program PROCESS on a mainframe computer and a printout of

the results is added in appendix

Absorption kinetics

2.1. 2

The

A-2.

relative

rate

of absorption of butenes into sulfuric acid

can be expressed by the following equation [9]:

x

where
gaseous

l-exp(-K*t)
K

(2)

is the absorption constant. K-values are mentioned for

and

liquified

butenes for various acid concentrations at

25C [10]. For a sulfuric acid solution of 80 wt-% at a temperature

of

25C,
3

xlO- min-

the
1

for

absorption
the

constant

has

the

value:

K=33.48

above mentioned mixture of liquified butenes.

The

relation

between

the

convers ion

percentage and the time is

shown in table (2-1):

Table (2-1): Conversion percentage of butenes at 25C
in 80 wt-% sulfuric acid.

(min)

10

Conv. %

20

28.45

48.81

2.1.3
For

which

30

40

63.37

50

73.79

81.25

60

120

180

86.59

98.20

99.76

Material balance
conversion

of

at least 98% at 25C, the residence time

is needed is 2 hours. For equimolar amounts of sulfuric acid

~

and butenes it is necessary to have the following flow rates:

-Amount of butenes

3,742.6

kg/hr

-Density of liquid butenes at 25C

602.09

kg/m 3

-Volume rate of liquid butenes

6.216

m3 /hr

-Amount of 80 wt-% sulfuric acid

8,032.54

kg/hr

-Density of sulfuric acid (80 wt-%)

1727.2

kg/m 3

-Volume rate of sulfuric acid

4.651

m3 /hr

2.1.4
During

Heat balance and cooling

the absorption an excess of energy is released which has

to be removed as adequate as possible to prevent the temperature to

rise

above

40C. If the temperature of butene, in contact with 80

wt-% sulfuric acid, rizes above 60C ,polymerisation will occur. To

prevent

any

polymerisation

in

the

system

the maximum reaction

temperature is set at 40C.

It

was

butylsulfate
sorber
the

not
and

possible to determine the molar enthalpies for the

the

deprotonated SBA in the effluent of the ab-

and the assumption was made that they had the same value as

molar

enthalpy for normal SBA. During the absorption sulfuric

10

acid
of

is

diluted from 80 wt-% down to 54.6 wt-%. The involved heat

mixing

is calculated as if the acid is diluted with water. The

formed absorption products are to leave the column at a temperature

of

40C.

To achieve this temperature, it is necessary to withdraw

an amount of heat Q of 2166 kW. It is not possible to withdraw this

heat

by

jacket
idea

the use of a jacket, filled with cooling water, because a

can

for

cooling

not
the

provide anough area for heat transfer. To give an

required

water,

cooling

calculations

area

were

and the required amount of

made

for two different cases:

cocurrent and countercurrent flow of cooling water through pipes in

the

column,

made

of stainless steel with a wallthickness d

of 2

mme

Foulingfactors:

inside

the

pipes:

= 5.7 kW/mz.oC for

hf(out) = 2.8 kW/mz.oC

hf(in)

treated cooling water and outside the pipes:

for inorganic liquids (12].
Heat

conductivity

coffint

for

stainless

steel:

ss

= 17

W/m.oC.
The overall heat transfer cofficint U becomes:

+ ---~-- +

ss

U
If
ing

= 1538

(3)

W/m z . oe

T(in) and T(out) are the temperatures of respectivily incomand

outgoing

temperatures
streams,

the

of

product

streams

respectivily

and

t(in) and t(out) are the

incoming and outgoing cooling water

logarithmic mean temperature difference ~Tln follows

from:

(4)

for countercurrent cooling and:

(T(in)-t(in-(T(out)-t(out

-----~-!I!~I=!I!~I==---------

T(out)-t(out)
for cocurrent cooling.
11

(5)

The required heat transfer area A can be obtained from:

Q
= ------

U. .1T
In

table

cooling

(6)

ln
(2-2)

water

.1T

,
cooling area A and required amount of
ln
mentioned as function of the outgoing cooling

are

water temperature.
table (2-2): .1T

, cooling area A and required amount of

ln
cooling water for co- and countercurrent cooling

water flow
countercurrent
t(out)

t(c.w.)

( Oe)

(m 3 /hr)

As
to

cocurrent

21

1861

9.94

142

10.49

134

22

931

8.96

157

10.15

139

23

620

7.82

180

9.81

144

24

465

6.34

222

9.46

149

25

372

9.10

156

26

310

8.74

161

27

266

8.37

168

28

233

8.00

176

29

207

7.61

185

30

186

7.21

195

can be seen from table (2-2) cocurrent coo1ing is preferabie

countercurrent

cooling

water

cooling.

flow

t(c.w.)

With

increasing

t(out) the required

decreases while the required cooling

area increases.
2.1. 5

With
area

Design

specific

costs

one

data about cooling water costs and heat transfer

can derive an optimal design. However, we assumed

12

- - - - - - - --

that

and

the

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

6T

of 8C is the minimum acceptable driving force for

ln
sufficint heat transfer and this fixes the cooling area at 176 mZ
cooling water flow at 233 m3 /hr. Another criterion is the

minimum
be

allowable

above

attain
tube

0.7

this

mis

to

prevent

fouling inside the tubes [40]. To

velocity, the water must flow through a total, radial

surface

tubes,

water velocity in the tubes. This velocity must

of

233/3600/0.7

= 0.0925

mZ Assuming a total of n

each with a height h, in the column, gives us the tube heat

exchange area A and the radial tube area A' as function of the tube
radius r:

*n *r *h

= 176
=2
n

A'

0.0925
= -----=n *
n

The

(7)

(8)

liquid butenes and the sulfuric acid are fed together in

bottom of the column with a total volume rate of 10.867 m3 /hr.

the
With

residence
3

21.734 m

time of 2 hours, the minimal required volume is

A column with a height of 13.7 mand a diameter of 1.5 m

provides

a total volume of 24.210 m3

to

13.7

m, eq.(7) and eq.(8) can be solved and give us the number

of

tubes

= 142

With the tube height h fixed

and the tube radius r

= 0.0144

m. The total tube

volume V
becomes:
tt

Substracting

this

value

remaining

absorber

residence

time

for

from

volume
the

of

the

total

22.566

butene-acid

m3

column

volume gives a

This volume provides a

mixture

of 2 hours and 4.6

minutes and a maximum butene absorption of 98.48% at 25C.

At

40C

the

absorption constant K is not known, but it can be

assumed that absorption at that temperature will be complete.

2.1. 6

Af ter

the

Gas-liquid separator
absorption

column the pressure is reduced to atmos-

pheric and although but ene absorption is considered to be complete,

a

gas-liquid separator is attached for removal of small amounts of

13

unreacted
them

gases.

We assumed these gases to be butenes and recycle

to the entrance of the compressor.

If the feedstock, however,

containes small amounts of inert ia as butane, a part of the recycle

is

to

be

purged

to

prevent

a build-up of these inert ia in the

absorber.
In

general

1iquid.

The

gravity

is

used

for

the

separation of gas from

maximum horizontal vapor velocity U

v in the separator

is calcu1ated with the fo1lowing equation [21]:

= 0.035

Uv
where

Pv

liquid
0.53
of

and

(kg/m 3
mis.

).

( (Pl-p v )/ Pv )
PI

are

(9)

the densities of respectively vapor and

For our system the maximum vapor velocity becomes

We want to remove a maximum of 2% of the initial amount

butene,

what

results

in

gas flow rate of 0.008 m3 /s. The

minimum

area for vapor passage then becomes 0.015 mZ The height h

between

the

must

be

top

is

the (horizontal) vessel and the liquid level

the vessel radius R. Using this data, the vessel

of

20%

diameter

of

calculated

gas

bubbles

of

the

minimum

vessel

at 0.60 m. With a slip velocity for small

1 cm/s, the residence time becomes 54 seconds and

volume for the liquid only 0.147 m3

Together

with the required gas volume, the total vessel volume becomes 0.164
m3 and the vessel length 0.60 m.
2.2

Hydrolysis tank

2.2.1

Material balance and design

Af ter
contains

the

absorption

partially

of n-butenes in sulfuric acid the liquid

deprotonated

SBA and secondary butyl sulfate.

Both components are completely and instantaneous converted into SBA

when

excess

water

is

added

to the liquid. The sulfuric acid is

di1uted from 36.8% by moles (80 wt-%) down to 6.8% by moles (30 wt-

%). At this dilution all intermediates are converted to SBA.

The
65.5
total

feed

of the hydrolysis tank contains 65.5 kmo1es/hr HzSO.,

kmoles/hr
flowrate

SBA
of

and

46.8

kmoles/hr water. This represents a

11,774.5 kg/hr. The density of this mixture is

derived with the following equation:

14

(10 )

Because

we

hydrolysis

have to deal with highly corrosive sulfurie acid, a

tank

is designed in which the fluid is not mixed by an

agitator with a shaft and inevitable seals, but in which the liquid
is

mixed

by

the impuls of the incoming water stream. Racz et.al.

[13]

stated

that the mixing time of an aqueous solution in a tank

with

approximately equal diameter D and height H can be calculated

with the following equation:

(11)

where:

= tank diameter
= nozzle diameter
= velocity of the
= mixing time

D
d
v
t

(m)
(m)
water in the nozzle (mis)
(s)

With the following data:

-Density of productstream

1370

kg/m 3

-Flowrate of productstream

8.542

m3 /hr

dilute the acid to 30 wt-%

14.483

m3 /hr

-Assumed nozzle diameter (2 inch)

0.0508

-Assumed tank diameter

0.5

15.16

-Volume rate of the water to

we obtain the following results

-Mixing time (t )
m
-Residence time (1.5*t )
m
-Volume of the tank

22.73

0.145

m3

-Height of the tank

0.740

2.2.2
Wh en
dilution

Heat balance

sulfurie

acid

is

heat is involved.

diluted

with

water a large amount of

It can roughly be estimated that in the

15

feed

one

product

mole

of

stream

HZ S04

leaving

is solved in two moles of water. In the

the

hydrolysis tank however, one mole of

HZ S04 is solved in thirteen moles of water. The molar enthalpy

a

mixture

with

HZ S04

kcal/mole
is

-211,19

acid-water

ratio

of

one

to two is -204.55

and for an acid-water ratio of one to thirteen it

kcal/mole

HZ S04

[19J.

By

diluting

the acid in the

tank an excess of 6.73 kcal/mol HZ S04 (28.20 kJ/mol) is

hydrolysis
~

an

for

released. The total heat product ion becomes:

65.5 kmoles/hr HZ S04

The

=
=

1.847*10

kJ/hr

513.11 kW

feed enters the hydrolysis tank with a maximum temperature of

40C. If we assume the temperature of the water stream entering the

tank

to

be 25C, the temperature of the productstream leaving the

hydrolysis

tank

deprotonated
danger

is

51.4C .

butylalcohol

for

Af ter

is

polymerisation

dilution all butylsulfate and

converted

of

the

into SBA and there is no

butene derivates. The product

stream can now be heated to 91C (boiling temperature of the waterSBA

azeotrope

at 1 atm.) and fed to a stripper where SBA and acid

are separated.
2.3

SBA stripper

The product stream leaving the hydrolysis tank is a mixture with

86.34 mol-% water, 6.83 mol-% secondary butyl alcohol and 6.83 mol%

sulfuric acid.

from

each

In this mixture acid and SBA have to be separated

other.

It

was

not the intens ion to obtain one of the

components in its pure form.

to

its

high

dissociated
libria

of

It was assumed that sulfuric acid, due

boiling point (338C) and due to the fact that it is

in

SBA

water, did not take part in the vapor-liquid equiand

water.

With

this assumption only the binary

system SBA-water is left.

To

define the number of equilibrium stages in the stripper, the

grafical

method

of

McCabe-Thiele

described with the data in fig.(2-1)

16

is

used. The binary system is

[25J. A part of this figure is

magnified and presented in fig.(2-2), together with the q-line, the

work
line and the equilibrium stages which are obtained. As can be
seen
in this figure, the azeotropic vapor separates in two liquid
phases and distillation can not go beyond the first separation
point (x
sba = 0. 1 40 , Ysba = 0.396).

(1) 2-BUTANOL

C4H 190

(2) WATER

H20

+++++ ANTOINE CONSTANTS

(1)
(2)

7.47429 1314.188
8.07131 1730.630

PRESSURE-

760.00 MM HG

CONSTANTS:
MARGULES
VAN LAAR
WILSON
NRTL
UNIQUAC

A12
3.9182
3.7964
11814.8851
639.8173
350.171l7

EXPERIMENTAL DATA
T DEG C
Xl
Yl
87.80
87.69
87.911
87.1111
87.IlII
87.19
87.29
87.4Il
87.59
87.611
87.70
88.10
88.10
911.20
92.70
93.80
95.80

0.11110
1l.1l2411
11.31111
0.3320
11.3619
11. 4781l
11.51411
11.5629,
11.58411
0.61140
11.6520
0.6840
0.71100
0.860"
0.91411
0.93110
11. 961111

11.36211
11.38211
1l.39611
11.3960
11.39611
11.4999
9. 4 lil 11
11.42211
11.42611
11.4360
0.45011
11.4640
0.48411
0.6219
0.7160
0.7580
0.8400

186.500
233.426

REG ION +++++

25- 120 C
1- 190 C

1.al3 BAR
A21

ALPHA12

1. 2808
1.4144
1643.6524
2491. U63
309.5428

0.4385

MARGULES
DIFF T DIFF Y1

WILSON
DIFF T DIFF Y1

VAN LAAR
DIFF T DIFF Y1

NRTL
DIFF T DIFF Yl

UNIOUAC
DIFF T DIFF Yl

-7.32
-3.78
2.114
1. 95
1. 86
1.97
2. lil
2.27
2.32
2.34
2.08
2.10
1. 85
-1. 02
-1.36
-1. 21
-1.10

1l.1996
11.9946
-11.11450
-11.11369
-0.9265
11.9961
11.9199
11.9296
9.9397
11.9367
0.0352
0.0337
0.11442
-11.0045
-11.9249
-0.0239
-0.0277

-3.33
1.12
1. 56
1. 53
1.51
1. 58
1. 69
1. 61
1. 58
1. 53
1.15
1.12
0.87
-1. 30
-1. 25
-1. 91
-0.84

11.11763
-1l.II257
0.0063
11.11112
0. U61
II.92U
9.9241
11.9237
11.112112
11.0224
Il.0134
Il.0983
0.1ll76
-0.1ll89
-0.9258
-0.9210
-0.9203

11.38
9.22
0.21
0.23
11.26
11.35
9.411
11.47
0.49
0.511
0.31
9.44
11.28
-0.80
-0.56
-0.33
-11.29

-".U22
9.0979
-0.0054
-0. ""82
-11.9123
-9.11289
-11.11269
-".9274
-9.9299
-11.11263
-0.93112
-11.11303
-11.9183
-0.0154
-0.11194
-0.11937
-11.111137

-2.22
1. 79
11.56
9.57
11.58
9.62
9.64
9.66
11.66
0.64
0.39
9.49
11.31
-0.82
-11.51
-0.26
-0.211

11.9474
-0.9394
11.11115
11.0102
9.91172
-9.9115
-9.11115
-11. U511
-0.U911
-Il. U68
-0.0237
-0.0258
-11.0147
-0.0158
-11.0091
-11.0018
-11.99118

-3.53
1. 96
1. 64
1. 61
1. 59
1. 66
1. 79
1.72
1. 70
1.66
1.30
1.28
1.114
-1.14
-1.14
-Il.92
-Cl.79

MEAN DEVIATION:

2.27

0.9417

1. 44

11.11219

0.38

II.1ll74

0.70

0.0165

1. 50

0.9193

MAX. DEVIATION:

7.32

0.1906

3.33

9.1l764

C.81l

II.1l303

2.22

0.0474

3.53

0.9819

1.00

0.80

0.'0

lL

YI

lL ~ K<

D.40 .c~

0.10

0.00

O~

O~

lL

'f

"

V
NRTl

Y Y I

O~

O~

XI

figure (2-1)

lL

/ I

51.95
5.12
O~

I~

McCabe-Thiele diagram for the

system SBA-water at 1.013 bar

17

9.9819
-9.9243
II.0U1
1l.9957
9.9193
9.U59
1l.9195
II.92U
0.U7l
0.1l198
9.11121
9.91189
1l.1ll76
-0.9157
-0.0230
-1l.9186
-1l.9188

Ysu
0.3

1."/

0./

tI./O

..."
) t -

SBA

figure (2-2): part of McCabe-Thiele diagram

from fig.

(2-1)

The separation configuration is as follows:

over the top the binary azeotrope of SBA and water is withdrawn.
Practically all alcohol is withdrawn this way.
- the bottom product consists only of water (and acid).
- there is no reflux and no condenser in the top.
there

is no reboiler. Vapor and energy are supplied by means of

steam injection in the bottom of the column.

The slope of the equilibrium line for x

"'sba * Psba
= 1x = ----------p

sba

0 is given by:

(12 )

At 100C,
P:ba = 771.3 mm Hg, p = 760 mm Hg and "'sba = 51.95. The
K-value becomes 52.72. If we want to evaporate 65.5 kmol/hr SBA, an
energy

of

converted

758.4
to

kW

water

is
of

required.
100C

If steam of 1900C and 3 bar is

and 1 bar, the enthalpy

change is

42.577 kJ/mol. For SBA evaporation an amount of 64.12 kmol/hr steam

is

to

be

condensed. To form an azeotrope with molefraction SBA

0.396,

an

amount of 99.9 kmol/hr water vapor is required. A total

feed

rate of 164 kmol/hr steam of 190C and 3 bar is sufficint to

18

strip

the

SBA

from

V in the stripper of 164 kmol/hr and a liquid flow L of 957.5

flow

kmol/hr.

For

<

sba
factor S becomes:
S

the water-acid mixture. This implies a vapor

* ~ = 9.02

=K

For

0.005 the K-value is constant and the strip

constant

(13)

S,

the fraction f of not stripped SBA on a tray,

compared with N trays above this tray is calculated with:

(14)

= 0.0733 and as can be seen in fig.(2-2), af ter two

f
stages the x decreased to 0.004. In table (2-3) the compositions of
The

liquid

and

vapor

are given for each tray. The trays are numbered

from the top down.

table (2-3): Tray number N and SBA fraction in liquid (x)
and vapor (y).

The
Murphree

0.073

0.396

0.040

0.395

0.004

0.211

4.0e-4

0.021

4.4e-5

2.3e-3

4.8e-6

2.5e-4

5.4e-7

2.8e-5

6.0e-8

3.2e-6

number of equilibrium stages is 8 and with an assumed (low)

tray efficincy of 60% the actual number of trays used in

the column is 13.

19
-

- - --

2.4
If

Caustic scrubber

the

entrained

demister

on

acid-mist

the top of the alcoholstripper fails,

(max.

0.05

the

kgf kg vapor) must be removed by

another technique. This is necessary to prevent deactivation of the

catalyst
like

used

most

for the convers ion of SBA in MEK. This catalyst is,

catalysts,

reactor

input

diluted

sodium

0.05*6653

stream.

kg/hr

sensitive for small traces of sulfur in the

The

hydroxide

vapor

is

therefore

scrubbed with a

solution. The maximum acid-mist flow is

332.65 kg/hr. This mist contains maximal 28.55

wt-% acid (acid concentration in feed stripper), so a maximum of 97

kg/hr
flow

HZ S0 4
of

has

to be removed.

For this a NaOH-solution (9 wt-%)

465.3 kg/hr is needed. The diameter of this column, based

on 70 percent of the flooding velocity,

20

is 1.0 m.

2.5

Sulfuric acid reconcentration unit

2.5.1

Reconcentration processes

Sulfuric
in

acid

acid reconcentration processes can be classified

high-temperature

and
High

in

vacuum

processes,

operating at atmospheric pressure

processes, operating at reduced temperatures [15].

temperature processes have their major use in reconcentrating

acid with organic contaminants, which must be reduced to the lowest

possible
acid

the

because
the
small

level.

For large scale concentration of relatively clean

vacuum

system

is expected to be the process of choice,

of the minimum air pollution possible. For reconcentrating

sulfuric

acid

leaving the acid stripper and which contains a

amount of secondary butanol,

is choosen for the Chemico drum

concentrator as a high-temperature process

[16J,

coo .....

-J. . ,

....---__, :w d ,f,f:i ,n

oovc, ac ..
Hw . . . . ,

_,t

eo.cI.' '''.'

. , . . . . IICI
. . . ~.L. ""'

Figure 2-3 Simplified flowsheet of Chemico drum concentration process.

21

The ehemico drum concentrator is used for concentrating sulfurie

acid

solutions

(2-3),

In this process, as shown in figure

hot furnace gases are contacted with the acid in a serie of

vessels

arranged

liquid
pipes

up to 93 wt-%.

countercurrently.

The

gases are blown onto the

at approximately the liquid level through silicon iron dipand

the

vapors

leaving the concentrator are scrubbed in a

venturi scrubber. The operating temperature is reported to be about

50C

below

the

atmospheric

boiling

temperature

of

the actual

mixture.
2.5.2
It
acid
the

is

Drum design
necessary to use two drums to reconcentrate the sulfurie

coming

from the acid stripper from 28.55 wt-% to 80 wt-%.

In

first and largest drum a reconcentration from 28.55 wt-% to 50

wt-%

is

achieved.

In the second drum the remaining acid stream is

concentrated upto 80 wt-%.

First drum:
The reconcentration from 28.55 wt-% acid to 50 wt-%
-The boiling temperature for
123

oe

-Operating temperature

73

oe

-Amount of water to be vaporized

9,646.9

-Heat required for evaporating water

6.234

-Heat of mixing (to be added)

0.109

MW
MW

6.343

MW

50 wt-% acid solution

kg/hr

-Tot al amount of heat required

(for the first step)
Second drum:
The reconcentration from 50 wt-% acid to 80 wt-%
-Boiling temperature for 80 wt-%

196

oe

-Operating temperature

146

oe

-Amount of water to be vaporized

4819.5

kg/hr

-Heat required for evaporating water

2.847

-Heat of mixing

0.546

MW
MW

3.393

MW

-The total amount of heat required

(for the second step)

22

The

total

amount of heat required for reconcentrating the acid

stream is 9.736 MW.

2.6

SBA purification unit

2.6.1

Liquid-liquid separator

Wh en

the

SBA-water

densed,

the

formed

liquid tends to separate into a light organic

heavy

inorganic phase. The upper liquid layer has a

phase
mole
a

and

fraction x b

s a,u

mole

fraction

obtained
fluence
two

in

vapors

from the caustic scrubber are con-

1 of 0.460 (77.8 wt-%) and the lower layer has

xsba,ll of 0.040 (14.6 wt-%). This separation is

liquid-liquid

separator

and occurs under the in-

of gravity, owing to the difference in density between the

liquids

separation.

[22J.
The

Horizontal

required

drums

residence

are generally used for this

time

(min.)

can

be ap-

proximated with the formula:

(15 )

with
the

the

viscosity of the dispersed phase (cP) and PIl and Pul

densities

dispersed

of

phase

lower and upper layer respectivily (g/cm 3

).

The

is the heavy, water-rich, phase and the viscosity

of water at 90 0 e is 0.3147 cP. At 90 0 e the densities of SBA and HzO

are

respectivily

0.78347

g/cm 3 and 0.96534 g/cm 3

the density of

the upper layer is calculated as:

0
(wt-%) * Psba
= x_______________________
_
sba (wt-%) * Psba + x h A______________

100
and

has

value

the

0.9388

value
g/cm

0.8238 g/cm 3

(16)

The lower layer density has the

The required residence time is t

= 8.21

min.

With a total flow rate of 1.832 kg/s, what is equal to 0.0022 m3 /s,
a

minimum separator volume of 1.085 m3 is required. With a length-

diameter

ratio of 4, the separator diameter is fixed at 0.70 mand

the length at 2.80 m.

23

2.6.2
In
for

Azeotropic distillation unit

figure
the

(2-4) are two McCabe-Thiele diagrams presented, both

binary

heterogeneous

system

HzO-SBA

at

1.013

One

bar.

predicts a

azeotrope [25] and the other a homogeneous azeotrope

with liquid-liquid separation beside the azeotrope [26].

1.00

0.10

0.10

YI

0.40

o.ZO

0.00
0.00

o.eo

0.80

V
NRTL

Y Y -I

0.20

0.40

0.20

51.95
5.12

0.10

0.10

XI

figure (2-4):

0.00
0.00

1.00

y'

NRTL

Y Y I

0.40

0.10

XI

..

AV

o.ro

VI
/ /

A ~

YI

1.00

V1

71.31
5.05
0.10

1.00

..

two different McCabe-Thiele diagrams for the

system SBA-water at 1.013 bar

In
a

theory it is possible to separate SBA and water if they form

heterogeneous

azeotrope.

azeotrope

Furthermore

and

the

not

if

difference

they

form a homogeneous

in boiling points is only

0.5C and separation by normal distillation is for this reason only

very

difficult.

ganic
a

To

solvent (entrainer) can be added to the mixture, which forms

light-boiling

the

azeotrope.

fractionation
with
is

ternary azeotrope and is by this way able tobreak

If

split

in

columns

azeotrope
ganic

is

layer.

columns.

In

the

right

amount of solvent is added, in one

column the mixture can be split in SBA and a mixture

azeotropic

both

make an SBA-water separation possible, an or-

composition, while in a second column the mixture

water
are

and again the azeotropic mixture. The tops of

connected

splitted
Both
table

with a decanter, where the condensed

in a light organic layer and a heavy inor-

layers
(2-4)

are
four

then

recycled

as

reflux to the

entrainers are mentioned with the

properties of the azeotrope they form with SBA and water. As can be
seen, diisobutylene (2,4,4-trimethyl-l-pentene, further referred to
as

DiiB)

forms

an azeotrope with the smallest amount of water in

24

the organic
layer.

layer and the smallest amount of SBA in the inorganic

Azeotrope:

ComponenlS

Percent composition

~ .

In azeotrope:

Uppe:r
layer

Lower
layer

99.5
1122
100.0

85.5

27.4
52.4
20.2

~1.7

62.3
6.0

4.6
0.6
94.8

U
L

86.0
14.0

U
L

0.858
0.994

99.5
1420
100.0

86.6

56.1
19.2
24.7

65.0
23.0
12.0

10.0
0.2
89.8

U
L

86.0
14.0

U
L

0.816
0.981

a. 2-Butanol
b. Cyc10hexane
c. Water

99.5
81.0
100.0

67.0

a. 2-Butanol
b. Diisobutylcnc
c. Water

99.5
1026
100.0

77.5

19.0
70.0
ILO

20.0
78.8

9.01
0.5
91.0 I

U
L

92.0
8.0

U
L

0.736
0.987

..

a. 2-Butanol
b. 2-Butyl acetate
c. Water
a. 2-Butanol
b. Butyl ether
c. Water

..

table (2-4):

to

Spc:cific
gravity
of layers
or azeotrope:

. BP.

Compounds

Relative
volume of
layers
at 2o-C

BP.

computer

; 1.2

ternary azeotropes, containing water and SBA

program, provided by Magnussen et. al.

[34], is used

do the separation calculations. The algoritm of this program is

based

on

the separation calculations as presented by Naphtali and

Sandholm [35]: the equations of conservation of mass and energy and

of

equilibrium

linearized

overflow
predict
the

are

by

then

is

obtained

by

energy

balances

are

stage and then linearized. These

solved

the

simultaneously.

Newton-Raphson

method.

Solution
In the

not taken in account, but equimolar

is assumed. The program uses UNIQUAC binary parameters to

activity cofficints. These parameters were obtained with

UNIFAC

columns

grouped

equations

convergence
program

are

group

T23

and

contribution
T29

plus

the

method.
obtained

Program

output

for the

UNIQUAC parameters are

presented in appendix A-4. The value for the molar heat of evaporation

of

DiiB

was

not

available and in the energy balance it is

given an arbitrary value Q.

25

In

the

figures (2-5) and (2-6) the component profiles in resp.

column T23 and column T29 are presented:

lIale fractian
1.8

DUB

8.5
SBA

H20

8.8*-~--~~~~~~~~~==~-,--~~~=-~-4
1 2
3
4
5
Ei
7
B 9
18 11 12 13 14
15 H.

tray na.

figure (2-5): component profile for column T23

(stage 1 is in the bottom)
.ale fractlan
1.8

8.5

8.8l-~~~---+--~--~==~~~~-=~==~--~
1

18
tray no.

figure (2-6): component profile for column T29

(stage 1 is in the bottom)

26

11

12

Methyl ethyl ketone product ion

3.1

Dehydrogenation reactor

3.1.1

Convers ion of SBA

There

are basically two paths to convert SBA into MEK. One path

is partial oxidation with oxygen:

SBA +
This

Oz -----) MEK + HzO

reaction is exothermic and a very good temperature control is

essential

to prevent uncontrolled reactions in which byproducts as

CO,

butenes

CO z ,

temperature

sufficint
oxidized

and

other

volatiles

control,

are

formed. Even with a

a large amount of the alcohol is

to HzO, CO and CO z . By using a catalyst as zinc-oxide the

temperature can be decreased to about 300C and the yield

reaction

of MEK from SBA can be increased to 75-80 percent. However, a large

amount

of the feed is turned into useless products which have also

to be separated from the MEK.

The second path is dehydrogenation of SBA by use of a catalyst:

SBA
This

_E~!.!._)

( ______ MEK + Hz

reaction is endothermic and the maximum convers ion depends on

the

equilibrium constant of the reaction. Because energy has to be

added, the temperature control is much easier. Furthermore hydrogen

is

formed

as

valuable

byproduct.

This hydrogen is of a high

quality because it doesn't contain non-condensables.

Depending
formed

on

due

the

used

catalyst,

undesired byproducts can be

to selfcondensation of MEK. These byproducts are of ten

unsaturated Ce-ketones like 3-methyl heptene-3-one-5, which are the

precursors

of

polymerisation

and

coking

on

the surface of the

catalyst, resulting in a rapid decreasing of the catalyst activity.

It

is

also

difficult to separate these byproducts from the crude

MEK.
In
of

the

this
easy

design is choosen for a dehydrogenation of SBA because

temperature

control,

27

the formation of high quality

hydrogen
bined

as

good

byproduct
activity

and because a catalyst was found that comand stability with a selectivity of 100% for

MEK.
Reaction thermodynamics

3.1.2
The

dehydrogenation

of

SBA into MEK is a gasphase equilibrium

reaction:

____KE___ >
SBA

Kp =

with:

<________

MEK + Hz

* p ( Hz)

p (ME K)

---p(SBA)-----

(17 )

Kolb and Burwell [17] derived three equations in which Kp'

6S

To

6H

To

and

were found as function of the temperature (T in K):

-2790
log K = ----- + 1. 510
p
T
6H
6S

In

To
To

= 12770 + 3.0

log T +1.865

*T
*

= 11. 54 + 6.908

log T

(18)

(cal/mol)

(19)

(cal/mol/K)

(20)

figure (3-1) the convers ion of SBA at equilibrium is plotted

as function of the temperature. Note that at a temperature of 200C

the maximum convers ion is
sion
large

increases

upto

SBA-recycle

~nly

93%.

60% and at 300C the maximum conver-

For

stream,

a satisfying convers ion without a

the reaction temperature must be above

300C.

28

SM cOllYllra i on

1.8,---------------:=::::===;8.9
8.8

8.7
8.6
8.5

8.4
8.3
8.2
8.1
8.8+-==~----_+----------+_--------

--------_+

__

4B8

188

figure (3-1): maximum feas ib Ie SBA convers ion

ai , Q.tw..

as function of the temperature

3.1.3
The

Catalyst choice

gas

phase

heterogeneous
selectivity,

dehydrogenation

catalysis.
good

Criteria

activity

and

for

of

SBA

is

supported

by

useful catalysts are good

good stability. Some examples of

licenced catalysts are:

-Raney
phase

nickel,

suspended

dehydrogenation

temperature

of

142C.

tetradecahydroanthracene

in tetradecahydroanthracene, for liquid

[27J. Provides a yield of 99.6% of MEK at a

Disadvantages

are

the

large

amount

of

(27 times the amount of SBA) required and

the slow convers ion (1.1 kg MEK per kg catalyst per hour).
-ZnO

with

Provides

Bi z 0 3

500C.

SBA

per

the

Feed rates are between 1.5 and 6.0 volumes of (liquid)

volume

af ter
SBA

[29J,supported on brass or steel.

yields of 58 up to 98% of MEK at temperatures between 400

and
that

[28J or Na Z C0 3

to

catalyst per hour. A catalyst example is reported

180 days of operation still converted more than 80% of

MEK. Catalysts are irreversible poisoned by traces of

water in the feed.

29

-Cu

with

CrZ03

and MgO on SiO z [30J. Provides at 260C a product

with 90% MEK, 5% SBA and 5% high-boiling byproducts. Adding 10 vol% water to the feed provides 95% MEK, 4.8% SBA and 0.2% byproducts.
Reported activity is stabIe over 6 months.
-Copper-tetramine
of

93

sion

complex

with 0.37% CrZ03 [31J. Provides a yield

to 96% of MEK at a temperature of 270 to 320C. Low conver-

rate

1 vol.

liq. SBA per vol. cat. per hour). Regenerated

with air at 350C and hydrogen at 250C.

-Cu

with

97.8%

BaCrO., CrZ03 and NazO on SiO z [32J. Provides a yield of

MEK at a temperature of 180C. Catalyst is also able to

of

convert di-secondary butyl ether to MEK.

-ZnO with 6 wt-% CeOz,ZrOz or ThO z [33J. Moderate reaction rate (up
to 6 vol. liq. SBA per vol. cat. per hour), and 1 to 14 mol-% heavy
by-products

formed.

Maximum

MEK

yield

about

96% at 400C, but

rapidly decreasing activity af ter 20 hours of use.

3.1.4
The

Kinetics of a Cu/Ni-catalyst
kinetics

of dehydrogenation of SBA over a catalyst with

composition

Cu:Ni:KzO:SiO z

Chanda

Mukherjee

and

(13.8:5.8:0.4:80) have been studied by

[18J.

Properties of this catalyst are men-

tioned in table (3-1):

154.9

. BET surracc area (S.)

Size
Average diameter (d,,)
Hulk density (Ph)
Pore volume (V.)
Porosity (~')
Average pore radius (r)
ParticIe bulk density (p,,)

table (3-1):
Analysis
surface

of

reaction

m~/g

- 48 + 65 Tyler mesh
0.02515 cm
0.7188 g/cm 3
0.4519 cm 3 /g
0.38
58.35 x I O-R cm
1.160 g/cm 3

catalyst properties

their
is

data

shows

that

a mechanism of dual-site

applicable over the entire temperature range

studied (250-310 0 C).

Below
320C

250C the conversion was found to be very low while above

the

convers ion

was
30

found

to

decrease

with

increasing

temperature.
products
ture

of

at

320C

it

was

in the tempera-

any

side-reaction

and

no

byproducts

were

in the reactor effluent. The catalyst which has been used

and above regained more than its original activity af ter
in

recommended
keeps

by

oxidized

decrease

due to fouling of the catalyst by reaction

250C up to 310C the dehydrogenation reaction was

accompanied

detected

was

formed at elevated temperatures. However,

range

not

This

with

activity
to

do

sufficint

air

at

350C.

Stability tests showed no

over a long period of time.

supplementary
activity

over

It is, however,

tests to make sure the catalyst

a period of two years when it is

only regenerated in the reactor with air at 350C when necessary.

Other

experiments,

which were conducted with catalysts of par-

ticle

sizes in the range of 0.25-1.0 mm diameter (d p ), showed that

the rate of reaction remained constant for particle sizes below 0.5

mm,

thus indicating the absence of internal diffusional resistance

below this size.

The initial reaction (p(H&)

= p(MEK) = 0)

SBA ------) MEK + H&

is
SBA.

first order reaction with respect to the partial pressure of

The

initial reaction rate ro can be fitted to an equation of

the form:
ro
The

values

mentioned

of

= ko
the

* p(SBA)

(21)

rate constant ko for several temperatures are

in table (3-2), together with the values for the activa-

tion energy.

31

table (3-2):

initial reaction rate constant ko at

various temperatures.
temperature (Oe)

ko (mol/g.hr.atm)

250

0.6279

260

0.7560

270

0.9340

290

1.1180

310

1.2830

Activation energy: 21.96 kj/mol

The reaction mechanism of the equilibrium reaction
K

SBA
is

) MEK + Hz

i-(----

one of a dual-site mechanism, with the adsorption of alcohol as

rate

limiting

step.

The

reaction

p(MEK)

* p(Hz)

rate

is

derived from the

equation:

ko
r

(p(SBA)

( r

in

In

the

Kp

(22)

mol
)
g.hr.atm
temperature

range from 270C to 310C the k-values are

given by (T in K):

= 2.70

kM

= 0.226

= 5.25

MH

*
*

* exp(

3.92

exp( 0.87

* 10
T

10-

10-

14

* exp(
32

10 3 )

(23)

3
(24)

15.74
T

3
10 )

(25)

Pressure influences

3.1.5

From eq.(22) it is obvious that with increasing SBA pressure the

reaction

rate

also

increases

while

with

increasing MEK and Hz

pressure the reaction rate decreases and the equilibrium changes in

favor

of

over

SBA.

the

In a tubular plug flow reactor a high pressure drop

catalyst bed would be useful for a fast initial reaction

rate (p(SBA) high and p(MEK) and p(Hz) both low) at the entrance of
the

reactor

and

reactor

(low

desired

pressure

high

total

degree

pressure,

drop

can

of convers ion at the end of the

in

favor

for

equilibrium). This

be obtained wether by high flow rat es

(disadvantage: short contact time, so large amounts of catalyst are

required

or large SBA recyle will occur) or by the use of catalyst

particles with small diameter (advantage: no diffusional resistance

limitations, resulting in efficint use of catalyst area).
The

pressure

Ergun-relation

drop
for

over

the

reactor is calculated, using the

the pressure drop over a bed of spherical par-

ticles for turbulent gas flow (Re> 700):

u z
g

Ap

with:

- voidfraction

(the

(kg/m 3

u - gas velocity
g
H - height of bed

(m/s)

d p - diameter of particles

(m)

lowest

Re-number

(26)

(-)

density of gas

p -

H
* -a-p

(m)

is

later on determined as 1382, what jus-

tifies the assumption of turbulent gas flow).

Pressure
degree

of

conversion
replaced
bitrary

and pressure drop in the reactorbed are related to the

convers ion

of

the

gas flow rate increases (one mole of SBA is

by
place

total

two
in

moles
the

SBA in the bed, because with proceeding

of

product). The reaction rate at an ar-

reactor,

however,

depends on the partial

pressures of SBA, MEK and Hz.

A
tion

small computer program is written to make an accurate estimaof

tube,
into

the

filled
a

expected
with

pressure

catalyst

particles. Therefore the tube is cut

great number of slices.

33

drop and convers ion in a reactor

In each slice the pressure drop is

calculated, assuming the SBA convers ion in the slice not having any
affect
is

on the total gas flow rate. At the same time the convers ion

calculated,

assuming

the pressure to be constant in the small

slice. Both gas flow rate and gas composition are then adjusted and
used

to calculate the pressure drop and the convers ion in the next

slice.

Main

variables in the program are the initial gas flow and

composition
diameter
among

and

have

other

initial

pressure.

fixed

values.

The output of the program contains,

things,

atmospheric)
Satisfying

the

the

final

Tube length and particle

pressure (must be slightly above

and the degree of SBA convers ion (must be above 90%).

initial pressures and flow rates are found by trial and

error. Af ter that, changing the number of slices then gives an idea
of

the

obtained

Pascal

and

is

accuracy. The program has been written in Turboto

be used on a personal computer.The listing is

presented in appendix (A-5).

3.1. 6

For

Design

sufficint heat transfer relatively small reactor tubes are

choosen

(diameter

0.10

mand height 0.85 m). Each tube is filled

with 4.800 kg catalyst and the maximum initial flow rate with which
a convers ion of 90%, at a temperature of 310C, is reached,
mol/s
per

(189.4 kg/hr). This implies a convers ion rate of 35.5 kg SBA

kg catalyst per hour. The initial pressure is 2.4 atm. To give

an

idea

flow

to

about

the

catalyst capacity, increasing the initial SBA

1.42

mol/s

and the initial pressure to 4.4 atm, gives a

of

85.6%

and

convers ion
catalyst
listed
of
kW.

is 0.71

per
for

hour.

In

a conversion rate of 67.2 kg SBA per kg

appendix

these two cases.

A-5

is also the program output

In the first case an amount of energy

23.84 kW must be added to the tube and in the second case 45.23
With

amount

of

diameter

total
28

initial

reactor

flow

tubes,

of 1.478 kg/s 99.8 wt-% SBA, an

each with a length of 0.85 mand a

of

0.10 m is required. The total heat flow from the furnace to the tubes must be 89.28 kW/m z tube area.
The minimum required wall thickess t

of a reactor tube is found

by the expression [41]:

t

(27)

with: R - external tube radius

(m)

p - pressure difference
over tube wall

(bar)
34

S - allowable metal stress

For
a

special Cr-Si-Mo alloys, used in furnaces,

value
With

m,

an

the factor S has

= 440

between 440 bar and 1220 bar. With S

= 0.10

and R

(bar)

bar, p

2 bar

becomes 0.4 mmo

initial

SBA flow of 0 . 71 mol/s the required energy in

first fifth part of the reactor tube is 14.84 kW or 278 kW/m 2

the
With

thermal

alloys)
tube
of

and

conductivity

of

17

W/m.oC (average for special

a wallthickness of 2 mm, the 6T over that part of the

wall must be at least 33C and the temperature on the outside

the

tube

800C,

heat

343C.

This is not a problem in a furnace, where at

transfer is for about 80% obtained from radiation and

for only about 20% from convection.

3.2
The
it

Hydrogen recovery

next

down

and

recovered
down

Af ter

that,

a
to

temperature

hydrogen
cooled

MEK

in

further

the

liquify
heat

the

major

product.

At

first heat is

exchanger where the effluent is cooled from

210C and the feed is heated from 99.5C to 197C.

the

temperature

In

to

in

3l0oC
feed

threatment for the gas leaving the reactor is to cool

effluent

is cooled down to 80.5C, the required

for

first MEK purification column. At this

and

the
SBA

are

gas-liquid

condensed

separator.

The

and

separated from the

remaining gas flow is

in two stages to remove the remaining SBA and MEK.

first stage it is cooled to 40C with normal cooling water

and

in

the

vapor

Pa.

The

hydrogen can therefore be withdrawn at a temperature of -

5C

and

approximately

vol-%.

the

If

further

second stage it is cooled to -5C with freon. At -5C

pressures of SBA and MEK are respectivily 97 Pa and 340

the

hydrogen

atmospheric pressure with a purity of 99.6

is

to be obtained with a higher purity,

cooling will not have much effect and it is better to wash

the hydrogen with a high boiling solvent.

3.3
The
are

MEK purification unit

components in the process stream which have to be separated

MEK, SBA and a trace of water. The trace of water made it very

difficult

to

separate SBA and MEK in one column. Simulations with

35

_ . __._-

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

PROCESS
could
and

with the binary system MEK-SBA gave no major problems. MEK

be

separated

yield

of

and obtained with a purity exceeding 99 mol-%

94

% in the top of a column with 30 equilibrium

stages and a reflux ratio of 3. Adding a trace of water (0.5 mol-%)

to the system made the MEK yield decrease to 51.8 %. Increasing the
number

of

stages

improvements.
which

means

and

the

reflux

All

the

water

that

the

bottom

ratio

showed

only

marginal

was found in the top of the column,

only

contained

binary SBA-MEK

mixture. In a second column this mixture could easily be separated.

Therefore
position
(T43)

two

columns we re simulated. Figure (3-2) shows the com-

profile

of

the

three

components over the first column

and figure (3-3) does the same for the two components in the

second column (T5l).

36

Mole fraction

1.B

B. 5

~
HZO

B.B
1

1B

15

ZB
tray no.

figure (3-2) : composition profile for column T43

(stage 1 is in the top)

MEK purification column T43:

20

Number of stages

Reflux ratio
Feed :

at stage

80.41

temperature

1. 06

pressure
composition:

Top:

89.46

mol-%

SBA

10.04

mol-%

0.50

mol-%

45.05

mol-%

78.31

oe

pressure

Bottom:

1. 00
98.15

mol-%

SBA

0.73

mol-%

1.11

mol-%

54.95

mol-%

87.65

oe

pressure

1.19

37

bar

MEK

Hz,O
rate, relative to feed rate
temperature
composition:

bar

MEK

Hz.O
rate, relative to feed rate
temperature
composition:

oe

bar

MEK

82.34

mol-%

SBA

17.66

mo1-%

Hz.O

0.00

mol-%

..ale fraction
1.8

8.5

8.8
1

figure (3-3):

18

15

28
tray no .

25

composition profile for column T5l

(stage 1 is in the top)

MEK purification column T51:

Number of stages

25

Reflux ratio
Feed:

3
at stage

temperature

82.18

pressure

1. 06

82.34

mol-%

SBA

17.66

mol-%

HzO

0.00

mol-%

rate, relative to feed rate

82.73

mol-%

temperature

79.38

oe

pressure

1. 00

composition :
Bottom:

bar

MEK

composition:

Top:

oe

MEK

99.31

mol-%

SBA

0.69

mol-%

17.27

mol-%

79.38

oe

rate, relative to feed rate

temperature
pressure
composition:

38

bar

1. 24

bar

MEK

1. 03

mol-%

SBA

98.97

mol-%

Voor-

IN

M
KtJis
'"
1.020;1

Massa-en
Warmtebal ans

waarts
Q

kw

Retour

k<J/s

Q
kW

11

1-'9.512

UIT

\.o'3.~6

C1

1-32.g,

:13.12
\. 0

~~

8 0 6.'Sl

6.20

'3~o.

\ot 2

~ ~ 0""\
Ct\. c.lt.

$0\\.\.

o~

67.A

~3o.

11

"o~') ~
~\6.~

43.2'2.

L/ 533 f.1

Ltl. '2 'l

1'14'6,~

'_3b 6

642~

2Ib6,'2
'3.26~6

6':1-72>

3.'2..501-

b
0'014

050

), 366

I l/3. 11

6~

.:,s

-- 5

r-------t

OO\~Cj

'2.2?,b

13.2..,\g

\\o~. \~

.. _. -

'2.2\6
\ 6 \~. '.14

'N\,+W\z Qs~ Qb
\- '~5'2' - 9P";j. 2.

Gis t Q(,
W'\,

V"t1l.

\~3.55

tlut

~r

~----I15

"'" , \- 'W\ t.

+-

\.6S2.1

Q.o'2.3

q!

..

3.

g6&'1

12l0.~tj

+ ll. 03'2.

CQs~ G7,
_ 551. \

05 ,

I~~. 2l

""'. +

t-CQ(,

-<3~~.?

vg

'Wj t

Lf22

<. oS

+.11~{,
lo~Lf

aS\

(441. b

12:J1G
23qq.~a,

o .

'Z 2

. . 12. .------1

TI4

2'2. '2.~.<6
\.'64-6
'L4~q.J

@-..

(,.'24'
'2. I 5". g'i

--. '8 .-----t

I
1

Q.

tLC;

G20

c) .

,.<6?>'Z.
2.<..(

55.6

20}----I

41

ILJ3

~u + 12?;r~

.
C'j.

L\-

756.1--6

<3.

L{

2G4~Ob

\. ~ '3 2.
566.3

v
\gX(-f
5.S)( (0- 1

\,

<O~'l..

~66.Lo.,
-~

<6
425.3

\,

'YY'\S'f-

'V't'\ ....

-e-

'5.I?-'2..
1266.6
Q1 + ~.'"

3~

-' -

T
2.~

Q~-4-

W\.~

Q....,

' y.f'\ ....,

5.4o~

Q'\ ~ Q"l ~C{1,~.~

o~3~
~,+ ,'3\. ~

--@----I

4.66~

G. + "308.3

Qsl-- Q,
,~'f.~

Q \,0) +Q~~
l
4- \ tass. <:,

o.2~5
~ .. Q,+~
.. +~g!

,......:L
T
~~
~
~~

WQ.~'t" ._

Qs\-

\-\

S\-e.o.W\

'2..ogQS

"n'\.s\-

Q)\. - Qtt
- {oS.':l'i

~L
Y1'\s'-

0504

Co~~", saJ~

30

---

l...6..

f Cf::J. g
4 -=1-q.qq
I (J~

I("Q

.k
37

, 41- g
1505.2.5

-...
..

3S

I. CJ~ ~

33

...

5'17.2

3ef

"
~I

F"

GIs

-'""e.\

....

36

~l\kt. ~"s
1"

""

Q - 2'2.4~$
s

---r-

\ .4~g
l~

W"\

2.

30

Ol"

-@
r~~\

--

I..
3~

\"-'..

~~t

l61..CO

(\1, - g6&.g
~+o. ~

R~~.,....
y..~

\ .q-+ '6

""t..

t'"

-~

311
~l.

14 :t~

I...-

4 =t4.~q

33

f.~9-'6
5~1.1

~B

35

'~

43

'lf:J!i?

ISos.15

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

- - - -- -

H
3.6

C.wQ.\e r

'3.6 \

6 o't. ~\

o 25

41.'119>

v /6

36.1-Z.

(l.JLf L

254.4

0'2.

H
O'

{b

16';f6

().o~6

Cl

S ('2.

T
Lf3

o. 3~4

lo$-i. I

o3~4

2., Lt. 5j.

\.

<"L~\,

<:;.'1$

166':/.S1

o 6'6

1\3.82

b
Z.

. ,. ( 6 ,
\S-?2.

c;-

____

@ __

-I

r-___-+_____~{-o-4~~
H

6tl5'

413

T
51

0 15

l.fq. 14

H
b

1413.

13,4

I I 2'6.

(J.

52. C~

050

2.9 g .(6

13.4

2251. ':)

55

....
V

-...

lO--

\,

,\

'lc,1.r

'54

0656
lott.2.

....... 1'"""

--

~I
~iI

H
o~3

6/.3l

c.wo..~r

...

5~

c., WCl.\tY'.

0'13

12.0.~f

HFit::

O~5b

45 ? s

r---

--r---

---

+- 2. W\S\ Glo+ 34>~+3C.)

+l"W\ .\- 2W\L ... 1 4l.s~ + 6,).,

W\",,-4- 2'W\~

W\'-I

too.6

11~~1,~

02 0 -t ~~,~ ~G la

-+ l'""t ~l~~~QLJ
"1""
+

~,~,

Massa in kg/s
Warmte in kW

Totaal

too, b

Fabri eks voorontwerp

No: 2.6Cj3

l~gljl.S

Apparaatstroom
, Compo'nenten
"A -

Bu...\-~ V\e.

+ltJ.5/2

. /.02.0':7

l.o3Cjb

806.'33

l.o~C)6

0.

l.o3lj~

:5

2
73281

'3

0.
3\6. Cj

o'''\~~

/3. 2..(j '3

0.'-4'-460
2. <l,ot{?

9-4.'14
5B~.Z'2.

3. 2.6Cj~

6'17. 2 5

S~l \).'f~c. ~

Wct.'e'('
~u.. \'" \ ~. \ ~oJl

--

Totaal:

1.02.01-

, Componenten
~u.. \-~ V\t

Su. \ ~X\ ('

("'Ar

0'0\
~(ll

Wf'l:\,~\",

~v..~v \Su..\ ~oJe

~(' ~\L'-'\ t'1. \('I\\\'o \

,.o3t)b

Apparaatstoom
V\ -

1'9.512-

'6~

1~2.81

',0~9

13.2.916

'.C)

3~~

o.o\~Cj

13.29B

316.

1Q

806.':> 3

'.9 g4
q ti 60
2. g cC{ f

o.

04460

':fC/.'f4

2.

SgC).21'l

~oqi

74. '/4

Lf.o2.3

. I

\0

iJ 22.

4.rttz

OOI;")'"

-.T

5S~. 2/

13LJ

20 l. 2-9

Totaal:

M in kg/s
Q in kW

3.2t'lt

611.25 o.o,gij

13.29&

3.25 0 1

663.'15

402. ~ .

Stroom /Componenten staat

4 'L 2.

1.2'1l/

lo lj 4

f Compo 'nenten
Sl.l\Ut"\L

OM

VJoJer
~c

I
~

gLl-~ ( a l(oho\

:t~Lf

'71

O{',. ....

.142

I,3llg

J"-.

20 l.

29

0.

M
I1-S4
4 142

,.

14

13

12

11

A pparaa tsTr oom

0.

3 4of KI

\'1 ';fo
4. lf '1 f-

'} (') U'J..

'

..

I?

~tJ'a

352.z6

-:;.2'1-4

23tj~.~q

o.~2.o

0.0

IS
0.
') I ~

...

J'1~O

I Q. I " !lOl

'2.o~~
o.

u,.,q

M
v

;r -'

gs

Totaal:

1 2'tf4

/09

o.

3L4ofgl

g20

6. 2.4 <6

21 Sl(o

89 3.{?6g

Igl()1~

oe::-

, Componenten
'S u. W""'f\c.. ...t.d

wnlpr"'

"':}'1
D 4- 46

Ig

li

16

APparaatstoom

Q
I

t. lil
.....

0.,4
J

M
I '7 ~PI

Q
11_'" T,/I

0446

B\.thl areola I
Sc.,..\:,l..,. U.., ,1,..", ',la

Totaal:

M in kg/s

<:).014

,.,/r.

I.

~q=l

[6

tG Iq. 9'1

2.2'3

ft 09. 1'1

---.S t

rn _L C

L..J'lO

1,'3Lt6

() n:Ln () n

~n

2q~4.3
~ n

4gs

1.341-

I 35 o. ~ S'
I,aS2.r

\. < 3 '2.

2q 55.6

/l05.2S

0.

lP

0.129

2.2

0.

I J 0 J.O)

0.495

Stt..

.-.~-,

2.0

1i}

c.

o Cl q
.::l ::l

Qo

Q()

S~L- DU~'l1

M
o

alCohol

24

23

.qgs

I 1'3 1-9

,.341-

386'51

Q
M
o S t 10-s "fjStl~l
1. 3 ~ fa-s 3. 6s 'u;'3

0485
'.'34'1

I ~ Cj.t6'g

/f?3z

sg(.5

2..

f Componenten
5tc.. ~~~'1'
0,'

M
0'0

0.. kb~O

i~ulc~.

84

\ 096'1
'3.21

2').2~

oSo')

2gl.

'6

M in kg/s
Q in kW

46 cr;

,.g ~

~.

:Su~.

'5

5{,6' 2~

M
161192 o'2...S
IC. 6 g o Cl 9s
o. I 6 5
~t..

6S
o 16';

ah -+

0'1-39

68

14 63.::}4

o.c,

g~

802.56

l.o'2.g

3. b'l.'

G1 -+- Q,

~. ~

5.1':/2.

64 43
14,41-

o.

\81.{

?l -\-

>z

_.~

t ~

....

Q,+G L t

5.40f.

g~.

'1

30
0.
'Lo z.43
6.0)

M
,,'6'1.(;)
/,326

0.

iS"

42Q.Sf"

'"

+GJ q t

oS04

Stroom
/Componenten staat
w_
_______
."" a .i i'

Z,

Z Cj:]. ~+
Q, + <V'l.

Q~

18 ~

02.15

lC)l. IJ

'2'l{63

M
04 g 3

'6 b

29

28

Q1 +

Totaal:

tlo-1

0.

0.0

0'')

M
o. Slj1

CV. +01

27

26

Apparaatstoom
\Na.~Y'

5663

I.g'f.( s 5 5

Cl

Di ,'so 1ovJ-(.,v\~

Totaal:

2S
I

, Compo'nenten
\i\hf-tr

22

2\

ApparaatsTroom

~_-.z=;~_

'

2b~.

qg

1,32.(?

42.5.1

WCl.~~Y"
S{Q. _~\~\ ~'Cb~O\

r\~~ . . .' ~"'V\\ tL.h,'\.(.

M
Oou \

I.

SI
411.6 <6

0'1

4:;~

0.0 0

3S

34

33

A pparaatsT'room
, Compo"nenten

1'2-

Loo 6

a.

M
0'00 \

1.<.f1-)
0'0011

Cl
4. 3 C;

l{.13g
ISol.((

1.6'7f

0001

IL/;f5
O 00 11..

sCO

3?-

17lJ./)
2.. 06

o . 00

6'

4.g9

'tt.{tJ6

I '2~1

'210.44
151.6 f

3(;

oltlC)
O 0

~",rt~ue>o..~

a.

00 \

t:).

L{, S

,qt]

3l.~~

,. 2 q I
o 0 1 ~

S 2.0'

'.lf:; ~

597-

o.

101.44

.j

Totaal: .

',4=1

wo..\-~y-

/. cf.:;. 8

M
0'\:>0\3

Sec- (3~a\c...'v\.o'

(). 'l.../ 9
Mt'~V\\ .f~~\ ~!"'" ,. 2l) I
O'o'lb
Uv.dy-o~

15 o S'lr

40

3~

APparaatstoom

f Componenten

Lf';}4.44

6137 '6 r
2'$.8'
41, t q

I,4:;g

1'1-3 0

41

U "

U
o.

036

43

00

'B

Cl.
-6 ~

I . 2 C, ,

3;1. '6'1
2($. g ~

"qq z

25~JI

'LC) . ~ 1-

42

0,os6

\ 6 2..

'4 tg

(lI-9

M
0'00

13.00

o.0'3J

(o'1-1t- '0'1 t}. 0 b

I.

?-

I.

g 06

S f L

"

Totaal:
M in kg/s
ct in kW

'41-'8

2.95. S 9

0'0

>b

2.t,47

~~s6_

o SI 2

Stroom /Componenten staat

ll'2l.g1

A pparca t

sTr oom

t Compo"nenten
Wcde.~

M
0.005

.S!c. _Bu.~\ n\Cn'-"n\ 0.0/37):1~\h~ ~. . .\ Y'.-\. ....... , /.-:;.8:J

4(,

45

LIet
'.64{,
3.01Lf
2/U,4g

a.

M
0.0\3 \'6

os 82

o.()oLi9

1.0'99

0.6 3 g

(0'2.

a.

.113

L(~

Lfi

0 ' 00\8
o.()oQ9

o.'So2...

063 g

46.Q?f

o ~t1f

47 1

o . S 63

a.

M
o. (44
Cl

653

(49

'36". 311
'2 q. q,

o-oUIZ

\6'. '1

o 15

o.

..J

Totaal:

18" 6

'" A pparaatsrroom
'- --

.~\\...."'\ ~\-"" ....\

V',\,.",~

Q.

M
017-

2. 4S'

io 4

o.~ q~

t.tq

f ComQonenten
S~c:...-Bv..\.~\ o.\c.~~o\

29/.2

50
M

l1-

13. Sb

O 0

, 5 o.j. ~1

2 -45 \

0. "
3~3.g~

M
1

4.66' Xl
0.652.

43. IS

,.00'

l49. ,4

52

51

~.gr

019:;

'.04

4 '6t )( (.; 1

{o? (6

0652.

a.

a.

b5~.r

44.11)"

Totaal:
r-.1 in kg/s

in kW

2.LJ6~

IS 20

' 1-

2..468

'3/11. ':f

0'656

Stroom /Comr

l 04,2.

0.656

QS .'2g

--_._ - - - -- -- -_._----

Apparatenli~st voor warm tewis selaa

fornu izen
--------- ----- ----- ----- ----- -----rs,
--------- --

H2

Appa raat No:

Benam ing,

CO"Y\.cl e-.t\S<I\.

type

Medium
pijpe n-/
mant elzijd e

Ccl ci~C;o\u..t~",

,,_10 \A..\-<'V\e

ft q
{oo

Ier

H \3

\-\ \~

\+eaJ-t/L

Cooler

04-( Ul.~oc{ + ~ a\ . ~ a(ec./

CCA.. Jl. SO \~\:, ~ ( S~e.o..~
C. W\U L
HzS

\-\ \ ~

H eateJL

NC1.0HI
CS \ (D.W"\

Capa citei t,
uitge wisse lde

Lf~<j.63

50

'3.'6

1305 Iq

\g~(\.~

/4.6

f,~

\/3

\/ \

warm te in kW.
Warm tewis selen d
oppe vl. in m2

26. /

21. 0

Aant al pafK lf{

'2-6. ~
o.

Abs. of eff. *
druk in bar
pijpe n- /
mant elzijd e

1/3

3/1

temp. in / uit
.
or.,
~n
pijpz ijde
mant elzijd e
Spec iaal te gebruik en mat.

So

'2.0

/40

\4b / 25

tt

/25

20 /40

52

I?. Vs 3 \~

i(

~\

l~o 1/30

\ I gg.!"
20 I qo

{(\J S1lb

aan~even

wat bedoe ld wordt

25 /~t
J~o 1130
e.VS

'S\b

H 211

H 2'1-

~e6<.:> ~ tUl.

[()Y\.c1 ~eIl

Appa raat No:

Benam ing,
type

Medium

b.u:l. cJ.c.uU/

pijpe n-/
mant elzijd e

S\-eo.W"\

30

1-1

c. wo..teAl
b~.a.O~
-+ ei .. ,su h.:i:L

,-

~e \ooae.n..

WaJeJL /
<t> \- ea. 0,1'

H 32

~S

\\ e.",-t

Co ol ClL
~.~)J

C.

vJ~

.ti C-~eJ'\.

W . J~".(

I\Eb z

Capa citei t,
uitge wisse lde

220

warm te in kW.
Warmte .... issel end

LI.

oppev l. in m2
Aanta l paf!lt~{

\ 0:$ 0

SS

Abs. of eff. i(
druk in bar
pijpe n- 1
mant elzijd e

/3

I I r

/ 9Qf'
13 0 1IJu

2.:> 14.:;

/3

\I\

I,

temp. in / uit
. oe,
ln
pijpz ijde
mant elzijd e

~9.r

~:;.s

I:;:; r

/00

I (cv

11.)IUo

CJ~.s

Il/o
IC/u

Spec iaal te gebruik en mat.

7(

aanee ven .... at bedoe ld .... ordt

99.1 11 =1-9
'3/0 12/;;)

Appa raat No:

Benam ing,
type

Medium
pijpe n-I
mant elzijd e

r- 36
'~U-

~~~.

cJc.t.e./

'~ ~J

3CO

C~~

Coo len-

c. watiA; c.
5J-~), +HEt

~o

\-\ q,

\-\- 4 <J

Coo \-eJL

eebo ',\u

(.AJ~I e~~/ ~~CJ.A el ... \0\.

H~cl(,,~

t\'do.(O~

s+eo..~

Capa citei t,
uitge wisse lde

2.25

~o \.

2..0

'Warmte in kW.
Wa=mte .... issel end
oppe vl. in m2
Aanta l pafl t{

,91..

/, '13

05

2.0 .

o. ~

842.. S
1\, ~

Abs. of eff. i(
druk in bar
pijpe n- I
mant elzijd e

2'-4 11

11

1 / 1

14

1 (1

\ (1

LO 11.4 0

-5/-~

?>B{8~

30. r I Cf

~o

temp. in I uit
. c,
l.n
pijpz ijde

\ '1'1-

mant elzijd e

Soo/ )JI.:l

3t.:>

2.:)

210 (

80 S"

{-5

130

I 1J0

Spec iaal te gebruik en mat.

i(

55

aan~even

wat bedoe ld .... ordt

~I Ll

Appa raat No:

Benam ing,

t-

C~eY\SVL

type

Medium

t-t

52

~Ioo~

\m.

c. wo1(/L! hJ alcoh~

pijpe n-I
mant elzijd e

I1E~

SteA W"\

<O~\b

1ll5 .

oppe vl. in m2

('b

L-6

Aant al pafI t{

H S5

H 51-

C~~~

Cao 1efL

Cao lOL

r\E.~

r\E~

C.

w~1

MEK

C. woleIL

H S~

C. WcJvt

Capa citei t,
uitge wisse lde
'Warmte in kW.
Warm te'Wis selend

Abs. of eff.

112..'3,

\ L{.

59

'3

,Lf

'56 . 1\ .Ll

l1

1 (1

-::t-qll-J o
Lo/q ."

15 / q0
LO l q lJ

druk in bar
pijpe n-

1I 1

mant elzijd e
temp. in
.

~n

I3

'1

11

uit

o~

pijpz ijde

'20( 4

105 1(0)

mant elzijd e

16/1-3

'5 0 /'Jv

?a 140

-=1-9 l1-ct

Spec iaal te gebruik en mat.

i{

aan~even

'Wat

bedoe~d

wordt

_---- -- .... __ ._-

Techn ische Hoges chool Delft

Afd. Chem ische Techn ologie

Fabri eksvo oront werp No: .2' ~ 3. .

Datum : g 11- .{ IqS t6. . . .
Ontwo rpen door . A.\-\: l.W\(. ''
Y?~E!11:~~I.ELMgsP~fI!:I~1:I~~~~
R, JA- (~~\-V'-

Appar aatnun nner : H.

2 .

Aanta l : .1. serie /para llel *

ALGEMENE EIGENSCHAPPEN :
Funk tie . . . . . :

Type

..........

TT
dtaiii'i
s

'~ aar
kesel

iC. alG!!

Konde nsor
Uuie .,,,,
Uitvo ering

.......

met vaste pijpp laten *

~,

11' .1jpj jp

1...
bhh

p2 'iuu e_'ilil Fklllls laar

..

Posit ie . .

horizo n taal/ 'u T'i Lh ur*.

'1-

Kapa citeit
Warm tewiss elend opper vlak

: .. 4 ~'\~
: . . .7..-6. \..

Overa llwar mteov erdra chtsc offic int

: . . 56S ".

.kW (berek end)

2
m (berek end)
2

Wim K(glo baal)

Loga ritmis ch tempe ratuu rvers chil (LMTD) :

14.3 . .. Oe
Aanta l passa ges pijpz ijde : 4
Aanta l passa ges mant elzijd e : 2
Korre ktiefa ktor LMTD (min. 0,75) .
: o ..tO o
Geko rrigee rde LMTD. . . .
: ..\~.H!i. o C

BEDRIJFSKONDITIES :
Mant elzijd e
Soort fluidu m . .
Massa stroom .

t'l ..

. kg/s

Massa stroom te ~~l~I. . /kondenseren~ .

.kg/s
Gemid delde soort elijke warmt e .
.kJ/k g .oe
Verda mping swarm te
. . kJ/kg
Temp eratuu r IN
Temp eratuu r UIT .
Druk . .
.

..

.... ........

.....

Mate riaal .

. bar

b. t;~

.\~o.q . .

..\.O c;.t ..
.

~. ~ 5

. .

Pijpz ijde

Ca. de ~ot~\~",
be'L' O . .

.. .
~

~.a 'i)

. '!SS - .
11 . . . . 2-.0. . .
. .4-a ..
. 3 . . . . . . 1 . . .
.S~uJ.. . .~~~ .
"

*Doo rstrep en wat niet

van toepa ssing ~s

57

Apparatenlijst voor reaktoren, kolommen, vaten

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

~----------~----------~----------r_--------~----------~--------~ I

Apparaat No:

V6

T3

Benaming,
type

Abs.of eff.*

druk in bar

~-----------+----------~----------~--------~----------~--------~ '

temp. in

oe

25-40

Inhoud in m3
Diam.

l46

2. 2. \
15

in m

1 of h in m

\ 11

liO
0

64

o.

blo

\.00

3.1-

52..

0150
0.50

\e ' f
01-66
~-----------+----------~----------~---------+----------~--------~ I
Vulling:

125

(l,bO

;{

schotels-aant.
vaste pakking
katalysatortype
-

,t

vorm

Spec iaa2. te

ge-

CL

bruiken ::lat.
aantal

LIS 1\(,

serie / :;:a:allel

aangeven wat bedoeld wordt

Apparatenlijst voor reaktoren, kolommen, vaten

---------------------~------------------------

Apparaat No:

f-\c.;d
Benaming,

t"\ tb

tl{

sh:p~.ljL

type

temp. in oe
Inhoud in m3

1
10 'l

'3\

~.S

in m

\. \ 0

1 of h in m

Vulling:

\0

L\',~

5..e.f~L

[) \~\: \~;J~~
ll\A""'" '1

~\

<j\

gfJ

"\

+.~S

1,08$

2 \. L

0,7

\. S

2,80

\'2.

020

1.

1..0

10

'.f.1. f

3(

schotels-aant.

\3

23

TMTP- ss
i>~~~

vaste pakking
katalysator-

ItoDM;-'.1 oll~-

type
- "

~lu.~>')

T 2.3

3(

druk in bar

Diam.

\I 20

A ~s\)( r\~0\'1 Li,\~

No..o t\
~\b"~

Abs.of eff.

17-

~~ 2.5

he,...

e.. V j

J {l.

- vorm

............
............
............

Speciaa.l te geb::uiken :nat.

aantal
serie / pa!'allel

R..

f- V5

V S 1 tb

316

aangeven wat bedoeld wordt

53

\Ct)

Apparaat No:

'-J 2t;

L\~~ -

Benaming,

\..t\~

type

~n

0c

Inhoud in m3
Diam.

in m

1 of h in m

Vulling:

S~.

O!~
S-\<5\o8f-

2,Q

1?-- ~

=1-7- r - loa

4-0

'2> \

2'b

1. (J

o-s"

la

'2.

~.'2..S

Lt~~

~~L
1
0

"

,01

2-0
0

25
.~

~1

30.)
0-0

/'"

025'
l . 2 S-

\3

vaste pakking
katalysator-

C"'/,{{ Oh );0,

S~~J

type

- " - vorm
.............
...... . .......
~

~~-

:;{

schotels-aant .

......

~6L

Cj 3"

3(

druk in bar
temp.

O\I)\~ \\~~~~

((.3'1-

\J ~~

Co \ u.."'" ""

~()j\J.\Abs.of effe

\" '2-'1

.........

Speciaal te ge-

Cl,-)l--Ho-

a/lo}"

b:-uiken ::lat.
aantal
serie ,lDa!'allel

3(

aangeven wat bedoeld wordt

60

Apparaat No:

O;St-; llo..t o~

Benaming,
type

V LIl,

T 4-3

UtSsJ

Co lu\'Y'\ Y'\

T5\
DiS\; \\o..\ttM

" 54
\J f! '>S~
!

[Qtw\.t)

I
Abs.of eff.

3{

druk in bar

temp. in oe
Inhoud in m3
Diam.

in m

1 of h in m

Vulling:

tg

-:tg - 2,<6
1

,
,

15

1 2.

ll,

'1-l3 -

l" S

150
I

19

1-9

36

IZ

2~

vaste pakking
katalysatortype

- ,,

- vorm

............

............
..... . ......

Speciaal te geb::-uiken :':lat.

aantal
se::::,ie / pa::::,al lel

1(

aangeven wat bedoeld wordt

I
I

2(

schotels-aant.

Techn ische Hoges chool Delft

Afd.C hemis che Techn ologie

Fabrie ksvoo rontw erp No: 1. b ~ '1

Datum : 1- /1- , \ Cj '6 fb
Ontwo rpen door : ' A. \-\. ~"1"'\~

R.. c4

TORENSPECIFIKATIEBLAD

Appar aatnum mer : T5

Fabrie ksnum mer :

ALGEMENE EIGENSCHAPPEN :
Funkt ie ..... ..... ..... :
Type toren ...
:

desti llatie /

Type schot el ..... ..... :

Aanta l schot els ..... .. :

k1.91-j

theor etisch :

"2..0

Aanta l schot els . ...... :

Schot elafst and / HETS :

prakt isch

'2..~

Diame t er toren ..... ... :

Mater iaal toren
:

......

Verwarming ..... ..... .. :

f"~ \ tA-

a_,liiiiiil~iliiii

8 R \ultE / schot el

o S m
\ .0

/ ;te

i~iiliiiii~1:

iipt:geilu~

/ zeefp laat /

Oi

Hilue- /

..... ..... ..... ..*

..... ..... ..... ...*
~~~

Mate riaal schot el :

Hoogt e toren

....

\~

W"\

s-\u i
~/

'ilfilOiiil

ij

e11111" / reboi ler /

..... ..... ..... .*

BEDRIJFSKONDITIES :

!
i

Voedi ng

, Top

Reflux/-eb~ol:p

Bodem

~e

Temp eratuu r ....

Druk ..

oe

bar
Dicht heid ...... . kg/m3
0

82>

,.

Massa stroom ..... kg/s

Samens tellin g ln
mol 7. resp. gew.7.

Se-.c.o~o\

EK

\Cj

5 0 1o . :}Cf t
"'" ,,/.

VI~.

*1-9

\05

:tij

\, '2.4

<005

C6lS
o \ S

o 6Sb
W\ '10
v'l.

\11-

\~

oob~

g'23

82

~Oj,J'

_.,.

w,I.

0,9

/,0 J

.mi ei/ .

80 S
\

..g

W\. " .

Oot ~8'~1 '1 Cf" J ,,bq

9~J

E~tt'e\tQ

Ifti:e:l

'\'1.J I

\
w 10

0':;
Cf'"

ONTWERP :
Aanta l kj

J '

/ zeef gaten /

.....
.....
..... ..... ...

Aktie f schot elopp ervlak .... - .

Lengt e overlo opran d ..... ....
Diame ter valpi jp /~ /

...** :

lo.fo

2
: o.bj m
:

~oomm

7
I!.\W\H R

T)l'5e flekki ttg ..... :

Hete!': tee:3: l' e:td~ iftg

AftHe tirrgcn pakki ng :

Verde re gegev ens op schet s verme lden

*doors trepen wat niet van toepa ssing lSo

**,ln d len
"
een toren schot els van versc hillen d

oncwe rp

d-~t~a~alin~g~e~v~e~nL.,
bevat J . ~l

Apparatenlijst voor pompen, blowers, kompressoren

--~----------------------------------------------

Benaming,

eS

c1

Apparaat No:

~"~'JJ

CCJWlfrt.,sS 0'-

type

f(~f

te verpompen

fl_

&>0 wt_o~
H2. S o~

b \A..t (..vU.

medium
Capaciteit in
t/d of kg/si(

'2,2- S

\.oLt
2.'50..\/

Dichtheid
in

3
kg/m ~

(./:r.e 1;:, ZI

c4~j
p~p

8a wt-%
HL 30 y

6.25

11-

PIS

~~~ ~~Jl
fu.~p
f tA.W"\f
Hz SOl\-

+ W.rJCb~

1. 2 1-

No..o~

I
0, lL~

\~OO

( 2 lq

I 15 Z

0 0

~l~ ~;p
in bar(abs.

'"

\0

3.2 S

~i()

temp. in

in / uit
Vermogen in kW
theor./ prakt.

25 / 1-1

lol.! (01..

5L

5 2

<3 \ I ~ 1

\ 0':>.3

R- tts

bruiken mat.
aantal

13. +/

Speciaal te ge

serie / parallel

ltf6 [ lqb

5l~

eVS J I ,

* aangeven

f..VS ~\b

wat bedoeld wordt

e.rlS 3l

Apparatenlijst voor nomuen. blowers. kompressoren

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

Apparaat No:

P '2. 2.

P 'LS

~j~ ~~j)

Benaming,
type

t>\.L~f

te verpompen

B~.

Jc.JJ.

+~~

medium
Capaciteit in
t/d of kg/s~

Dichtheid
in

P '2.. 1

\. g 1

g1- 0

kg/m 3

2 <

~~\\.\.~

~7JJJ ~J)
f~p

fu.~

~~-

cJea1J

~
B~_

gvl,- c..O(M + Di; \ u L..",,--:t-vf ....L-+ Oi

-+ Wa..tVL

,6 b C6

\3'1

3\5

131>

o1cv{)
~So b~

cdf,~
~

wa.i0-

-\-wo:ttA

-1-5 Cf

J1t

-s

loo

Zuig-/persdruk

1/1.5 .

in bar(abs.~

~!)
temp. in

I
0

B~-) (g~- )

Cj~.r / c,S, r

~1,r Itf')

in / uit
Vermogen in kW

theor./ prakt.

1- f~ s 19-t-;-

10.;)

! 1 o~

\~~

02

Speciaal te ge
bruiken mat
aantal
serie / parallel

* aangeven

wat bedoeld wordt

~EE~~~~~~!!~~~_~~~~_E~~E~~~_~!~~~~~~_~~~E~~~~~~~~

p ~q

Apparaat No:

P 42-

Benaming,

~J

type

~J

~J

r~p

~j
(?u -(J

~~.~

medium

Capaciteit in
t/d of kg/s*'
Dichtheid
in

kg/m 3

P q~

~ ~\v..'Jl .

pc.\.~p

te verpompen

P~ 5

M(~
o.f.!'

\ 131

, ,LJQ2

3\5

~o~

\1 Et:..
+ d1c.-~

I. \

~a ~

L\ C'j
J~.J
f7

f~

t---\ Et:

o6Qr
~oS-

rtE K
~ cJc~)

6.g
~o<

Zuig-/persdruk
in bar(abs.of
eff. *.)
temp. in

in / uit

qo

(C(o

So.)"{ 2a,~

1-8(1-~

7-2 (1~

~~ I F~

Vermogen in kW
theor./ prakt.
Speciaal te ge
bruiken mat
aantal
serie / parallel

* aangeven

wat bedoeld wordt

Apparaat No:

Benaming ,
type

te verpompen

p So

p'S1

P5b

~~jJ
fUY>'\f

~
~7J

~J

ftAf

B J- -cJc.o~ f5~ +.{J

medium

.J...

Capaciteit in
t/d of kg/si(
Dichtheid
in kg/m 3

t-\E~

o 15

\ , g\ \

SiS

3 0g

nE~

a66
~oS-

ZUig- / persdruk
in bar(abs.of
eff.i()
temp. in

in / uit

loS f{)

?-q

t 1-Cf 1-9

{1-cr

Vermogen in kW
theor. / prakt.
Speciaal te ge
brui ken mat
aantal
serie / parallel

* aangeven

66

wat bedoeld wordt

Cost estimation and economics

The

equipment

costs

prices

published

by

have

been

calculated,

the Dutch Association for Chemical Engineers

[24] and are given in the following tabie:

table (6-1): Equipment Costs
Equipment
Compressor and
cooler
Heat Exchangers
Columns

Number

Costs (f)

1
18

384,000

880,000

11

443,400

17

329,000

Furnace

42,000

Reactor

126,000

57

2,654,400

Tanks and
separators
Pumps

Total

according to the

The

total

capital

investment has been calculated by using the

method of H. C. Bauman [23] and is given in the following tabie.

table (6-2):

Total capital investment

Component

Ratio

Cost (f)

Purchased equipment

100

2,654,400

Equipment installation

47

1,247,568

Instrumentation

18

477,792

Piping

66

1,751,904

Electrical

11

291,984

Buildings

18

477,792

Yard improvements

10

265,440

Service facilities

70

1,858,080

159,264

346

9,184,224

Engineering and supervision

33

875,952

Construction expenses

41

1,088,304

Construction's fee

21

557,424

Contingency

42

1,114,848

483

12,820,725

86

2,282,784

569

15,103,536

Land
Total direct costs

Fixed-capital investment
Working capital
Total capital investment

68

table (6-3): Raw material costs

Material

Cost

Total cost

(t/yr)

(f/t)

(f/yr)

26,456.6

638

16,879,311

Sulfurie acid

290.3

150

75,996

Sodium hydroxide

300.9

500

,150,467

n-Butene

Amount

Total

17,105,724

table (6-4): Selling prices

Material

MEK
Hydrogen
SBA

Price

Total price

(t/yr)

(f /t)

(f/yr)

33,721.9

1750*

59,013,325

Amount

933.2

1800

1,679,616

1550

Total

60,692,941

*: Price obtained from Shell Nederland Chemie section Marketing.

A price of f 1750/ton was reported as normal although in
june 1988 prices increased to f 2100/ton and incidental
prices up to f 3300/ton where reported.

table (6-5): Manufacturing costs

Component

Ratio

Cost (f)

A.Direct production costs

(60% of total product costs)

60

31,101,316

33

17,105,724

10

5,183,553

1.Raw materials
(10-50% of p.c.)
2.0perating labor
(10-20% of p.c.)
3.Direct supervisory
(10-25% of operating labor)

1.5

777,533

4.Utilities
(10-20% of p. c.)

10

5,183,553

5.Maintenance and repairs

(2-10% of fixed capital)

1.5

777,533

0.2

96,155

1.5

777,533

2.3

1,192,212

6.0perating supplies
(0.5-1% of fixed capital)
7.Laboratory charges
(10-20% of operating labor)
8.Patents and royalities
(0-6% of p.c.)
B.Fixed charges
(10-20% of product costs)

15

7,775,329

4,146,842

C.Plant-overhead costs
(5-15% of p.c.)

D.General expenses

17

8,812,039

1,555,066

4,146,842

2,591,776

518,355

100

51,835,527

1.Administration
(2-5% of p.c.)
2.Distribution and sel1ing
(2-20% of p.c.)
3.Research and development
(5% of p.c.)
4.Financing
(0-7% of total capital)
Total
Income

60,692,941

Gross annual earning

Two

statie

economical

methods,

justified,

8,857,414
used

are

for

the

deciding

pay-out

if

a n investment is

time calculation and the

return on investment calculation.

The pay-out time (POT) is defined as the minimum required number
of years, necessary to repay the original investment. As is assumed
that

the working capital is returned af ter ending the project, the

original investment only consists of the fixed capital investment:

POT = gE~_~~~~~l_~~E~!~K ___ _
fixed capital investment
This

assumption

is

not

made

when

(28)
calculating the return on

investment (ROl). The ROl is defined as:

ROl

= grQ~~_~~~~~l_~~r~!~g ______________________
fixed capital investment + working capital

* 100%
(29)

For this project the POT is 1.45 years and the ROl is 58.6%.
The

internal

rate

of

return (IRR) is an example of adynamie

method. With this method the cash flows,

inc1uding the investments,

over the entire life time of the project are converted to this very
day

with

a return fraction r. The sum of all converted cash flows

must be zero and this can be obtained by changing r.

7'

For this project the 1ife time is fixed at 10 years and the rest
value

RV

of

the

equipment

investment

F.

Furthermore

earning

is

constant

returned

af ter

is fixed at 10% of the fixed capita1

it

over

is
10

assumed

that the gross annua1

years. The working capita1 W is

10 years. The converted cash flow over a period of

10 years is:
-F -W +

+r

(+r)Z

...

(+r)g

E+RV+W

(30)

(+r)o

Solving this equation with:

12,820,725

=
=

8,857,414

RV

1,282,073

gives

2,282,784

va1ue

for

of

72.

0.58187

and

IRR

of

58.2%.

REFERENCES.
1

Kirk-Othmer, "Encyclopedia of Chemical

Technology",vol.13,Wiley Intr.Ed.

(1984)

G.A.Chernyshkava and D.V.Mushenko, J. Appl.

Chem. (USSR), 53(11), 1834 (1981)

Hydrocarbon Processing,48(11),204 (1969)

Kirk-Othmer, "Encyclopedia of Chemical Technology",

vo1.4,Wiley Intr.Ed.

(1984)

C.B.Dale, C.M.Sliepcevich,and R.R.White,

Ind. and Eng. Chemistry, 48(5), 913 (1956)

Petroleum Refiner, 36(11), 264 (1957)

Petroleum Refiner, 38(11), 272 (1959)

Chemical Engineering, Feb. 8, 63 (1960)

H.S.Davis ,J. Am. Chem. Soc., 50, 2780 (1928)

10

H.S.Davis and R.Schuler,J. Am. Chem. Soc., 52, 721 (1930)

11

R.C.Weast,"Handbook of Chem. and Physics" ,

The Chem. Rubber Co.

12

(1971-1972)

R.H.Perry and C.H.Chilton,"Chemical Engineerings Handbook",

McGraw-Hill Int. Book Co.

13

(1974)

J.Racz, J.G.Wassink Hnd P.Dees, Chem. Eng. Tech.,

46(6), 261 (1974)

14

E.E.Ludwig, "Design for Chemical and Petrochemical plants",

vo1.2, Gulf Publishing Co.,

(1964)

15

I.Rodger, Chem.Eng.Progress, 11(2), 39 (1982)

16

G.M.Smith and E.Mantius, Chem.Eng.Progress, 17(9), 78 (1978)

17

H.J.Kolb and R.L.Burwell jr., J.Am.Chem.Soc., 67, 1084 (1945)

18

M.Chanda and A.Mukherjee, J.Appl.Chem.Biotechnol.,

28, 119 (1978)

19

D.D.Wagman and W.H.Evans,

"Selected Values of Chemical

Thermodynamics Properties", National Bureau of

Standards, Washington (1968)
20

"WEBCI/WUBO prijzenboekje", Dutch Association of Cost

Engineers, Leidschendam (1986)

21

J.M.Coulson and J.F.Richardson,"Chemical Engineering",

vol.6, Pergamon Press (1983).

22

L.Ricci, "Separation Techniques 1: Liquid-Liquid Systems"

McGraw-Hill Publ. Co. ,New Vork (1980).

23

M.S.Peters and K.D.Timmerhaus, "Plant Design and Economics

for Chemical Engineers", McGraw-Hill Publ. Co., N.Y.

24

(1958)

Ullmanns, Encyklopdie der Technischen Chemie,

4, band 9 (1975)

25

Y.Yamamoto and T.Maruyama, Kagaku Kogaku, 23, 635 (1959)

26

I.N.Bushmakin, A.P.Begetova and K.I.Kuchinskaya,

Sintet.Kauchuk, 4, 8 (1936)

27

US pat.no. 2,829,165 (1958)

28

US pat. no. 2,436,970 (1948)

29

US pat.no. 2,835,706 (1958)

30

German pat. no. DT 2,347,097 (1973 )

31
32

German pat. no. DT 1,026,739 (1958)

German pat. no. DT 1,913,311 (1969 )

33

British pat.no. 663,376 (1949)

34

T.Magnussen, M.L.Michelson and A.Friedenslund,

IChE Symp.Series 56, Proc.Int.Symp.on Dist.,
London (1979)

35

L.M.Naphtali and D.P.Sandholm, AIChE Journal,

17(1), 148 (1971)

36

J.Gmehling, U.Onken and W.Arlt, Vapor-Liquid Equilibrium

Data Co11ection, vol.1 (suppl.1), Dechema (1981)

37

A.G.Montfoort, De Chemische Fabriek, deel IA: Flowsheettheorie en ontwerp, Collegediktaat TUD, Delft (1980)

38

A.G.Montfoort, De Chemische Fabriek, deel 11: Economische

aspecten en cost-engineering, Collegediktaat TUD,
Delft (1980)

39

F.J.Zuiderweg, Fysische Scheidingsmethoden, Collegediktaat

TUD, Delft (1980)

40

concept diktaat Apparaten voor de Procesindustrie deel 4:

apparaten voor warmteoverdracht, Collegediktaat TUD,
Delft (1980)

41

W.L.Nelson, "Petroleum Refinery Engineering",

fourth edition, McGraw-Hill Publ. Co., N.Y.

7'1

(1958)

Appendix
A-I

Chemical and physical properties

table (1):

Antoine constants

In (p) =
Component

p in mm Hg and t
A

in K.
:temp. range

C
15.785

2299.6

-22.77

15.737

2932.1

-52.55

+1 - +100

SBA

17.210

3026.0

-86.66

:+25 - +120

DiiB

18.585

3984.9

-39.73

-2 - +127

MEK

16.264

2904.3

-51.19

: +20 - +120

n-butene

: -73

+27

Tab1e(2): Chemica1 and physica1 properties

Methyl Ethyl Ketone
-Molecular weight

72.10

-Boiling point at 1 atm.

79.57

-85.90

-Freezing point
-Refractive index,

1. 378

-Density at 20C

804.5

kg/m 3

-Surface tension at 20 0 e

24.6

mN/m

-Specific heat of vapor at 137e

1732

J/kg. oe

-Specific heat of 1iquid at 20C

2084

J /kg. oe

2435

kJ/mole

-279.5

kJ/mole

32.8

kJ/mole

-Critical temperature

260

-Critical pressure

4299

kPa

-Viscosity at 20C

0.416

mPa.s

-Heat of combustion at 25C and

constant pressure
-Heat of formation at constant
pressure
-Latent heat of vaporization at
79.6C and I atm.

-Flash point

-1

-Solubility in water at 20C

27.5

c
wt-%

-Electrical conductivity at 20C

2*10"

pS/m

Secondary Butyl Alcohol

-Molecular weight

74.10

-Boiling point at 1 atm.

99.5

-Freezing point'

-114.7

-Refractive index,

1.39446

-Density at 15C

810.9

kg/m 3
J/kg. oe

-Specific heat of vapor at 137C

-Specific heat of 1iquid at 20C

c
oe

2730

J/kg. oe

-268.1

kJ/mole

-Heat of formation at constant

pressure
-Latent heat of vaporization at
99.5C and 1 atm.

41. 687

kJ/mole

-Critical temperature

265

-Critical pressure

4850

kPa

-Viscosity at 15C
-Flash point

42.10

mPa.s

24.4

-Solubi1ity in water at 30C

18

c
wt-%

71

n-Butene (2 % l-butene. 89 % trans-2-butene.

9 % cis-2-butene)
-Molecular weight

56.11

-Boiling point at 1 atm

0.99

-110.1

-Freezing point
-25
-Refractive index, n
D
-Density of liquid at 25C

602.09

kg/m 3

-Density of gas at OoC and 1 atm

2.591

kg/m 3

-Surface tension at 20C

0.01356

mN/m

-Specific heat of vapor at 25C

1550

J /kg. c

647.1

kJ/mole

-9.443

kJ/mole

21. 60

kJ/mole

-Critical temperature

155.9

-Critical pressure

4147

kPa

1.3868

-Heat of combustion at 25C and

constant pressure
-Heat of formation at constant
pressure
-Latent heat of vaporization at
lOC and 1 atm.

Sulfuric acid
-Molecular weight

98.08

-Boiling point at 1 atm

338

-Melting point

3.0

-Density of liquid at 25C

1.841

kg/m 3

-Surface tension at 20C

50

mN/m

-Specific heat of liquid at 20C

1443

J/kg.oC

-811.2

kJ/mole

-Heat of formation at constant

pressure
-Critical temperature

655

-Critical pressure

8208

kPa

A-2

Stream data compressor Cl

VERSION 0484
***********:::
SM
PROCESS

INPUT LISIING - PAGE

GENERAL DATA
TITLE USER=A\
AND R
,PROBlEM=CCMP,PROJECl=FABONI,DAIE=FEB87
DIMENSION SI,TEMP=C,PRESS=BAR
PRINT \.lTO fIletl
COMPONENT DAIA
LIBID 1,BUI1/2,BTC2/3,BTT2
THERMODYNAMIC DATA
TYPE SYSTEM=SRK
STREAH DATA
PROPERTY STRM=1,TEMP=25,PRESS=1.0,PHASE=V,*
COMP (M)=1,2.0/2,9.0/3,89.0,NOCHECK,RAIE(M)=66.7
UNIT OPERATICt\S
COMPRESSOR UID=Cl,NAME=BUT-CO~PRESSOR,KPRINT
FEED
1
PRODUCT L=2
OPER
PIN=1.O,POUT=3.2~,PCLY=76,TESl=40
COOLER
DP=Q.25,TOUl=25

VERSION C484
SIMULAIION SCIENCES, INC.
PROJECT FAEONI
PROBLEt1 Cm1P

PRCCESS

SM
PAGE
A.

SCLUTION

Ar~D

7
R

FEB87

SUMMARY OF COMPRESSOR/EXPANDER/PUMP/IURBINC UNIIS

1 UNIT Cl
, BUI-COHPHESS, IS A CCMPRESSCR

***
***
***

FEED STREAHS ARE

1
LICUID PRODUCT IS SIREAM 2
OEERAIING CONDITICNS

TEHPERAIURE, DEG C
PRESSURE, BAR
ENTHALPY, MM KJ . /HR
ENTROPY, KJ j~OLE DEG C
MOLE PERCENT LIQUID
ADIABAIIC EFFICIENCY, PERCENT
POLYTRCPIC EFFICIENCY, PERCENT
ISENTROPIC COEFFICIENT, K
POLYTROPIC COEFFICIENI, N
HEAD,M
ADIABATIC
PGLYT:lOPIC
ACTUAL

INLET

ISENTRC!?IC

OUlLE!

25.00
1.000 0
2.638 1
216.3 610
0.000 0

60.82
3.250 0
2.835 9
216.3 510
0.000 0

71.01
3.250 0
2.903 5
219.3 471
0.000 0
74.56
76.00
1.112 1
1.152 9
5391 .95
5496 .42
7232 .14

'WORK, KW

THECRETICAL
POLYTROPIC
ACTUAL
COHPONEt\TS
1 THRU

54.98
56.04
73.74
-

2.664 0E+0 0

CC~PCNE~T

2.137 4E+0 0

AFTERCCCLER
DUTY, MM KJ /HR
TEHPERATURE, DEG C
PRESSURE, EAR
1 THRU 3
9.948 3E-0 1 7.321 8E-0 1

90

KVALUES -

2.224 7E+0 0
1.762 4
7.721 9E-0 1

25.00
3.000 0

VERSION C484
SIMUlAIICN SCIENCES, INC.
PROJECI FtWONl
PROBlEM Cm1P

PROCESS

SM

PAGE 10
A.
AND F..
FEB87

SOLUTION
SIREAr1 SUMMARY

STREAM ID.
NAtiE
PHASE
FROM Ul\IT/TRAY
TO UNIT/TRAY
FROM SlREM1

M KGS/HR
MOLECULAR ~EI(HT
STD lIQ
M3/HR
DEG API
SP GR
KGS/M3
UOP K
REDUCED TEMP
REDUCED PRESS
ACENTRIC FACTOR
**VAPCRl)*
M KGS/HR
MOLECULAR ~EIGHT
STn LIQ
M3/HR
SID ~
M3/HR
ACTUAL H M3/HR
KGS/fo!
M3

CP,KJ IKG MOL C

**LIQUID**
M KGS/HR
MOLECULAR ~EIGHI
SID lIQ
r13/HR
ACTUAI GPB
~13/HR
~GS/~3

IKG MOL

VAPOR
Ol 0

LIQUID
11 0

1/

KG MOlS/HR
TEMPERAlURE, rEG C
PRESSURE, BAR
H, MM KJ /HR
M KJ /KG MOlE
KJ IKG
MOlE FRACT LIUID

CP,KJ

66.700
25.000
1.000
2.638
39.551
104.913
0.00000

Ol

66.700
25.000
3.000 - 1.141
17.107
304.893
1.00000

3.742
56.108
6.134
99.965
0.6113
610.0669
12.926
0.695
0.025
0.217

3.742
56.108
6.134
99.965
0.6113
610.0669
12.926
0.695
0.075
0.217

3.742
56.108
6.134
1.495
1.610
2323.841
0.97403
8.9201E+01

0.000
0.000
0.000
0.000
0.000
0.000
0.00000
C.COOOE+OO

0.000
0.000
0.000
0.0000
0.000
0.000
0.00000
O.OOOOE+OO

3.742
56.108
6.134
30.4500
6.916
541.125
0.01255
1.3545E+02

r;

A-3

Stream data SBA stripper T14

N 0484

SH

SIHULATION SCIENCES, INC.

PROJECT FAI30NT
PROBLEM ACID

PROCESS
A

SOLUTION

STREAtl COl1PONENT FLOU RAIES -

PAGL 12
AND H

Jl\N87
KG

11OLS/HH

STRSAM ID
NArE
PHASE

LIQUID

'JAPOR

'/APOR

LIQUIU

1 WATER
2 SBUOH
3 SULFURIC

827.6753
65.4740
65.4740

164.0000
0.0000
0.0000

99.7643
65.'1085
0.0000

891.9106
0.0655
65.4740

958.6230
51.4'.)00
1. 0000
4.3971
1.0000
0.0000

164.0000
190.0000
3.0000
8.2191
0.0000
0.0000

165.1728
9:.0728
1.0000
0.9086
:J . 0000
0.0000

957.4500
101.5943
1.0uOO
7.7576
1.0000
0.0000

IOTALS
IEHPERATU~E,

~EG

PRESSURE, BAR
H, MM KJ /HR
HOLE FRACT LIQUID
RECYCLE CONVERGENCE

A-4

Data azeotropic distillation unit

SYSTEM H20-SBA-DiiB at 760 mm Hg

NUMBER OF COMPONENTS
3

COMPONENTS
1
H20
SBA
2
3
DiiB
ACTIVITY COEFFICIENT:

O=NONE, 4=UNIQUAC

UNIQUAC BINARY INTERACTION PARAMETERS

0.000
259.551
779.367
-73.656
0.000
259.935
331.969
105.468
0.000
UNIQUAC SURFACE AND VOLUME PARAMETERS
5.616
3.924
0.920
4.920
3.664
1.400
ANTOINE COEFFICIENTS
15.737 2932.149
17.210 3026.030
18.585 3984.922

8s

-52.545
-86.660
-39.734

NUMBER OF STAGES
16
NUMBER OF FEEDS
2

THE STAGE

~T

WHICH FEED 1 IS INTRODUCED

THE VAPOR FRACTION OF FEED 1

0.000000000000000
COMPONENT FLOW RATES IN FEED 1
26.920000000000000
18.170000000000000

0.0000000000000

THE STAGE AT WHICH FEED 2 IS INTRODUCED

12
THE VAPOR FRACTION OF FEED 2
0.000000000000000
COMPONENT FLOW RATES IN FEED 2
4.660000000000000
12.990000000000000
CONDENSER ( YIN)?
Y

THE DISTILLATE RATE

77.120000000000000
THE REFLUX RATIO
4.200000000000000
NUMBER OF LIQUID SIDE STREAMS

NUMBER OF VAPOR SIDE STREAMS

THE PRESSURE
760.000000000000000
ESTIMATE THE TOP AND BOTTOM STAGE TEMPERATURES
IN DEGREES CELSIUS
77.000000000000000
99.000000000000000
THE MAXIMUM CHANGE IN TEMPERATURE
BETWEEN ITERATIONS ( DEGREES CELSIUS) - OFTEN 10
2.000000000000000
THE MAXIMUM FRACTIONAL CHANGE IN FLOW
RATES BETWEEN ITERATIONS - OFTEN 0.5
0.100000000000000

31.5700000000000

EQUILIBRIUM STAGE DISTILLATION SIMULATION

COMPONENTS:
1:H20

2:SBA

NUMBER OF STAGES
DISTIl,LATE RATE
RE FLUX RATIO
TOTA1 PRESSURE
STREAM

3:DiiB
16
77.120
4.200
760.000

FLOW RATE

TeC)

17.19
77.12

99.6
73.7

BOTTOMS
DISTILLATE
STAGE

T(C)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

99.60
99.60
99.58
99.51
99.25
98.37
95.60
89.25
84.85
84.26
84.24
83.95
83.94
83.89
82.91
73.66

COMPONENT FLOWS
0.0000
31.5800

LIQUID FLOW

17.1896
13.9704

0.0004
31.5696

COMPONENT FLOWS

17.19
418.21
418.21
418.21
418.21
418.21
418.21
418.21
373.12
373.12
373.12
373.12
323.90
323.90
323.90
323.90

0.000
0.002
0.009
0.037
0.147
0.580
2.269
8.611
4.443
1.900
1. 488
1. 759
1. 633
1.674
2.525
17.144

17.190
418.175
418.070
417.687
416.288
411.242
393.887
342.718
222.825
153.336
138.482
138.637
123.504
123.294
122.902
115.989

0.000
0.037
0.134
0.490
1.779
6.392
22.059
66.886
145.856
217.888
233.154
232.728
198.767
198.936
198.477
190.771

FLOW CONFIGURATION
I
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

FL
17.2
418.2
418.2
418.2
418.2
418.2
418.2
418.2
373.1
373.1
373.1
373.1
323.9
323.9
323.9
323.9

FV
401.0
401.0
401. 0
401.0
401.0
401.0
401.0
401.0
401.0
401.0
401.0
401.0
401.0
401.0
401.0
77.1

SL
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

85

SV

FKV

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

FEEDSTREAMS
0.0
0.0
0.0
0.0
0.0
0.0
0.0
26.9
0.0
0.0
0.0
4.7
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
18.2
0.0
0.0
0.0
13.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
31.6
0.0
0.0
0.0
0.0

*K-FACTOR
* * * * *IN *COLUMN
* * * * PROFILE
* * * 72.'3
******
1
')

.:...

3
4
5

6,.,

8
9
10
11
12
13
14
15
16

4.141
4.141
4.140
4.136
4.123
4.079
3.958
3.798
6.035
13.911
17.937
17.568
16.444
16.457
15.588
7.737

1.000
1.000
0.999
0.996
0.987
0.955
0.862
0.681
0.644
0.846
0.938
0.923
0.898
0.897
0.854
0.506

3.805
3.804
3.801
3.789
3.746
3.599
3.162
2.274
1.390
0.996
0.929
0.921
0.937
0.934
0.905
0.695

NUMBER OF STAGES
12
NUMBER OF FEEDS
1
THE STAGE AT WHICH FEED 1 IS INTRODUCED

6
THE VAPOR FRACTION OF FEED 1
0.000000000000000
COMPONENT FLOW RATES IN FEED 1
28.250000000000000
0 . 880000000000000
CONDENSER ( YI N)?

Y
THE DISTILLATE RATE
3.840000000000000
THE RE FLUX RATIO
4.200000000000000
NUMBER OF LIQUID SIDE STREAMS

NUMBER OF VAPOR SIDE STREAMS

THE PRESSURE
760.000000000000000
ESTIMATE THE TOP AND BOTTOM STAGE TEMPERATURES
I N DEGREES CELSIUS
73.660000000000000
99.600000000000000
THE MAXIMUM CHANGE IN TEMPERATURE
BETWEEN ITERATIONS ( DEGREES CELSIUS ) - OFTEN 10
2.000000000000000
TH E MAXIMUM FRACTIONAL CHANGE IN FLOW
RATES BETWEEN ITERATIONS - OFTEN 0.5
0.100000000000000

1.4700000000000

EQUILIBHIUM STAGE DISTILLATION SIMULATION

COMPONENTS:
1:H20

2:SBA

NUMBEH OF STAGES
DISTILLATF. HATE
HEFLlJX HATIO
TOTAL PHESSUHE
STHEAM

1
2
3
4

5
6

8
9
10
11
12

12
3.840
4.200
760.000

FLOW HATE

T (G)

26.76
3.84

101.5
77.2

BOTTOMS
DISTILLATE
STAGE

3:DiiB

T(C )

COMPONENT FLOWS
26.7579
1.4921

LIQUID FLOW

101.46
101.43
101.35
101. J5
100.54
97.10
96.96
96.22
93.24
87.84
84.42
77.19

0.0021
0.8779

0.0000
1.4700

COMPONENT FLOWS

26.76
46.73
46.73
46.73
46.73
46.73
16.13
16.13
16.13
16.13
16.13
16.13

26.758
46.717
46.697
46.646
46.514
46.117
15.901
15.813
15.361
13.557
10.326
8.332

0.002
0.011
0.031
0.082
0.208
0.508
0.191
0.277
0.720
2.475
5.467
6.187

0.000
0.000
0.000
0.000
0.006
0.103
0.036
0.038
0.047
0.096
0.335
1.609

FLOW CONFIGUHATION
I

FL
1
2
3
4
5
6
7
8
9

la
11
12

26.8
46.7
46.7
46.7
46.7
46.7
16.1
16.1
16.1
16.1
16. 1
16.1

FV
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
20.0
3.8

SL
0.0
O. 0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

SV

FKV

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0

FEEDSTHEAMS
0.0
0.0
0.0
0.0
0.0
28.3
0.0
0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
0.9
0.0
0.0
0.0
0.0
0.0
0.0

0.0
0.0
0.0
0.0
0.0
1.5
0.0
0.0
0.0
0.0
0.0
0.0

*K-FACTOR
* * * * PROFILE
* * * * *IN *COLUMN
* * * T'2...J
******
1
2
3
4
5
6
7
8
9
10
11
12

1.000
0.999
0.997
0.991
0.974
0.883
0.879
0.861
0.791
0.704
0.768
0.752

5.986
5.976
5.951
5.888
5.705
4.923
4.880
4.658
3.761
2.071
1.044
0.596

40.837
40.778
40.627
40.238
39.128
34.341
34.069
32.659
26.850
15.221
7.431
3.837

A-5

Program listing and output for

MEK convers ion reactor

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

Listing of MEK . PAS,

1:

page 1 at

U1:~3pm

U~/l1/~4

proeram MEK_conversion;

2:
3:
4:
5:
6:
7:
8:

9:
10:
11 :
12:
13 :
14:
15:
16:
17:
18 :
19:

const
MS
74.123;
MM = ?2.10?;
MH = 2.016;
R = 8.3144;
E = 0.32;

Var
T,Dk,Dp,Ks,Km,Kh,Kp,KO,W,dW,
Xs,Xm,Xh,
F,FO,Fs,Fm,Fh,FsO,
P,PO,Ps,Pm,Ph,
Ue,Conv,Rho,Ra,TubeLength,
TubeDia,Tau,G,H,S,Gr

i,j,N
PrinterEcho
Choice

Real;
Integer;
Boolean;
Char;

20:
21 :
22: Procedure Initialisation;
23: Beein
24:
T:=273.16+310;
25:
H:=53429.0+3*T;
26 :
5 : = 1 1 . 54 + 6 . 908':\- In ( T) I In ( 1 0) ;
27:
G:=H-T*S;
28:
Ok:=0.0005;
29:
Ks:=5.25e-14*exp( 15.74e3/T);
30:
Km:=0.226*exp(0.87e3/T);
31:
Kh:=5.25e-14*exp( 15.74e3/T);
32:
Kp:=-2790/T+1.510*ln( T) I1n( 10) +1.865;
33:
Kp:=exp(ln(10)i~Kp);
34:
KO:=1.3/3.6;
{mol/kg . s.atm}
35:
W:=TubeLength*pi/4*sqr(TubeDia)*718.8;
36:
dW:=W/N;
37: End j
38:
39: Procedure Input;
40: Beein
41:
TubeLength:=0.85;FO:=0 . 71;PO:=2.4;Xs:=0.998;
42:
Xm:=0.002;N:=1000;TubeDia:=0.10j
43:
ClrScr;
44:
GotoXYC5,4) ;WriteC 'Tube diameter (m)
') ;ReadCTubeDia);
45:
GotoXYC5,5);WriteC'Tube length Cm)
');Read(TubeLength);
46:
GotoXY(5,6) ;WriteC 'Initial flow (molis)
') ;Read(FO);
47:
GotoXYC5,7) ;Write( 'Initial pressure Catm)') ;ReadCPO);
48:
GotoXYC5,8) ;Write( 'Molf'raction SBA
') ;ReadCXs);
49:
GotoXYC5,9) ;WriteC 'Molf'raction MEK
') ;ReadCXm);
50:
GotoXY(5,10);Write('# steps
');ReadCN);
51:
GotoXY(5, 11) ;Write( 'Printout? C YIN)');
52:
Repeat read(kbd,Choice) Until UpcaseCChoice) in ['Y', 'N'];
53:
If' Upcase(Choice)='Y' then PrinterEcho:=True else PrinterEcho:=False;
54:
P:=PO;
55:
F:=FO;
56:
FsO:=FO*Xs;
57:
Ps:=Xs*P;
58:
Pm:=Xm*P;
59:
Xh:=O;
60 :
Ph:=O;
61:
Fs:=Xs*F;
62:
Fm:=Xm*F;
63:
Fh:=O;
64:
If PrinterEcho Then
65:
Begin
66:
Writeln(lst);

- --

_._---_.

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

Listing of MEK.PAS,
67:
68:
69:
70:
71 :
72:
?3:
74:
?S:
76:
77:
78:
79:
80:
81 :
82:
83:
84:
85:
86:
87:
88:
89:
90:
91 :
92:
93:
94:
9S:
96:
97:
98:
99:
100:
101 :
102:
103:
104:
10S:
106:
107:
108:
109:
'10 :
111 :
1 12 :
1 13:
, 14 :
11S:
1 16 :
117:
118 :
119:
120:
121 :
122:
123:
124:
12S:
126:
127:
128 :
129:
130:
131:
132:

Writeln(
Writeln(
Writeln(
Writeln(
Writeln(
Writeln(
End;
End;

lst, '
lst, '
lst, ,
lst,'
lst, ,
lst, '

page 2 at 01:33pm 07/11/84

Tube diameter
Tube length
Initial flow
Initial pressure
Molfraction SBA
# steps

" TubeOia:7:4,' m');

',TubeLength:7:4,' m');
',FO:7:4,' mol/s');
',PO:7:4,' atm');
',Xs:7:4);
, ,N:7);

Procedure Output;
Begin
ClrScr;
GotoXY(S,4);Write(j,'
pressure = ',P:7:4,' atm');
GotoXY(5,S);WriteC'
convers ion
',CFO-Fs)/FO:7:4);
GotoXY(S,6) ;WriteC'
rho = ',Rho:7:4,' kg/m3');
GotoXY(S,7) ;Write('
flow
' ,F:7:4,' mol/s');
GotoXY(S,8) ;WriteC 'reaction enthalpy = ',Gr/1000:7:4,' kW');
GotoXY(S,9) ;WriteC'
x(SBA) = ',Xs:7:4);
GotoXY(S,10);Write('
x(MEK) = ',Xm:7:4);
GotoXY(5,11);Write('
xCH2)
= ',Xh:7:4);
GotoXY(S,20) ;WriteC' Press key to continue ');
If Not PrinterEcho then repeat until keypressed;
GotoXY(S,20) ;WriteC'
');
If PrinterEcho Then
Begin
Writeln( lst);
Writeln( l s t , '
j*(N div S):4,':
pressure = ',P:7:4,
Write(lst,'
conversion = ',Fh/FsO:7:4);
Writeln( l s t , '
x(SBA) = ' ,Xs:7:4);
Write(lst,'
rho = ' ,Rho:7:4,' kg/m3');
Writeln( lst, '
x(MEK) = ',Xm:7:4);
WriteCIst,'
flow = ' ,F:7:4,' mol/s');
x(H2)
= ',Xh:7:4);
WritelnC lst, '
WritelnC lst, ,
reaction enthalpy = ' ,Gr/1000:7:4,' kW');
End;
End;
Procedure Kinetics;
Begin
Ra:=KO*(Ps-(Pm*Ph/Kp))/( 1+Ks*Pm+Km*Pm*Kh*Ph);
Conv:=dW*Ra;
End;
Procedure GasOensitYi
{kg/m3}
Begin
P: =P-:l-1 0 132S . 0;
Rho:=P/R/T*CXs*Ms+Xm*Mm+Xh*Mh)/1000;
P:=P/10132S.0;
End;
Procedure GasVelocity;
Begin

{superficial}

Ug:=F/(pi/4i~sqrCTubeOia))*(Xs*Ms+Xm*Mm+Xh*Mh)/Rho/1000;

End;
Procedure PressureOrop;
Begin
GasOensity;
GasVelocity;
Op:=1.7S*( 1-E)/(E*E*E)*Rho*sqr(Ug)*TubeLength/N/Ok/10132S.0;
End;
Begin
Input;
Initialisation;
Clr5cr;

Listin2 of MEK.PAS,
133:
134:
135:
136:
13?:
138:
139:
140:
141 :
142:
143:
144:
145:
146:
14?:
148:

149:
150:
151 :
152:

pa2e 3 at 01:33pm 0?/11/84

For j:=1 to 5 do
Begin
For i:=1 to (N div 5) do
Begin
GasDensity;
GasVelocity;
Tau:=TubeLength/N/Ug;
Kinetics;
Fs:=Fs-Conv;Fm:=Fm+Conv;Fh:=Fh+Conv;
F:=Fs+Fh+Fm;
Gr:=G*Fh;
Xs:=Fs/F;Xm:=Fm/F;Xh:=Fh/F;
Xs:=Fs/F;Xm:=Fm/F;Xm:=Fm/F;
PressureDrop;
P:=P-dP;
Ps:=P*Xs;Ph:=P*Xh;Pm:=P*Xm;
End;
Output;
End;
End.

Tube diameter
Tube length
Initial flow
Initial pressure
Molfraction S8A
# steps
200:

400:

600:

800 :

1000:

O. 1000
0.8500
0.?100
2.4000
0.9980
1000

m
m
mol/s
atm

2.2419
pressure
conversion
0.5613
rho = 2.226?
1 . 1o??
flow
reaction enthalpy = 14.83?0

atm
kg/m3
mol/s
kW

pressure
2.0294
conversion =
0 . ?456
rho
1 .8034
flow =
1.2383
reaction enthalpy = 19.?086

atm

pressure =
1 . ??26
conversion = 0 . 8310
1 . 5021
rho =
flow = 1 .2988
reaction enthalpy
21.9661

atm

kg/m3
mol/s
kW

kg/m3
mol/s
kW

pressure = 1 . 4602
conversion =
0 . 8?62
rho
1 . 2080
flow =
1 .3308
reaction enthalpy = 23.1615

atm

pressure =
1 .0505
conversion = 0.9020
rho
0.8583
flow
1 . 3491
reaction enthalpy = 23 . 8442

atm

34

kg/m3
mol/s
kW

kg/m3
mol/s
kW

x(5BA)
x(MEK)
x( H2)

x(SBA)
x( MEK)
x( H2)

x( S8A)
x( MEK)
x( H2)

=
=

=
=

x( S8A)
x( MEK)
x( H2)

x(S8A)
x(MEK)
x( H2)

0.28o?
0.3603
0.3590

O. 1456
0 . 42?8
0.4266

0 . 0922
0.4544
0 . 4533

0.0659
0.46?6
0.4665

=
=

0.0515
0.4?48
0 . 4?3?

Tube diameter
Tube length
Initial flow
Initial pressure
Molfraction BBA
# steps
200:

400:

600:

800:

1000:

O. '000
0.8500
1 .4200
4.4000
0 . 9980
1000

m
m
mol/s
atm

pressure
conversion
rho
flow
reaction enthalpy

=
4.0596
=
0.5209
=
4.1394
=
2. 1582
= 27.5389

pressure
conversion
rho
flow
reaction enthalpy

=
=
=
=

3 . 5986
0.6965
3.2905
2.4071
36.8259

pressure
3.0254
conversion = 0 . 7816
rho
2 . 6354
flow
2.5277
reaction enthalpy
41 .3232
pressure
2.2844
conversien = 0.8289
1 .9401
rho =
flow
2.5947
reaction enthalpy = 43 . 8227
pressure
conversion
rhe
flow
reaction enthalpy

atm
Iq~/m3

mol/s
kW

xC BBA) =
xC MEK) =
xC H2)
=

0.3146
0.3434
0.3420

xC BBA)
xC MEK)
xC H2)

0.1787
0.4113
0.4101

xC BBA) =
xC MEK) =
xC H2)

0.1224
0.4393
0 . 4382

xC BBA)
x CMEK)
x( H2)

0.0935
0 . 4538
0.4527

x( BBA) =
x( MEK) =
x( H2)
=

0.07?8
0.4617
0.4606

atm
kg/m3
mol/s
kW

atm
kg/m3
mol/s
kW
atm
kg/m3
mol/s
kW

1 .0998 atm

=
0.8556
=
0.9265 kg/m3
=
2.6325 mol/s
= 45.2333 kW

A-6

Stream data MEK purification column T43

VERSION 0484
SM
PROCESS

INPUT LISTING - PAGe

GENERAL DATA
TIlLE USER=]\
AND R'
, PROBLEM=MEK PURIF. ,PROJECT=FVO, DATE=E'ED87
DIMENSION SI,TEMP=C,PRESS=BAR
PRINl WTO PTION
COMPOriENl DATA
LIBID 1,MEK/2,SBUOH/3,~ATER
THERHODYNAMIC DATA
TYPE SYSTEH=SRK
SlREAM DATA
PROPERTY STRM=FD,PRESS=1.0,PHASE=L,*
COMP(M)=1,89.46/2,10.04/3,O.SO,NOCHECK,RATE(M)=72.07
UNIl OPERATIONS
COLUMN UID=ACOL,KPRINT
PARAMETER TRAY=20,FAST=5,SURE=30,DKDX
FEED FD,7
PRODUCT OVHD=ATOP,65,BTMS=ABOT,7.8
HEATER 1,20,4/2,1,-3
CONDENSER TYPE=3,PRESSURE=1.0
PSPEC TOP=1.01,DP=O.01
SPEC STRM=ATOP,COMP=1,1,FRACIION(Y) =0.99
VARIA3LE HEAT=1
PRIrJT TRAY=20
PLOT PROFIL~,XCOMP=1/2/3,YCOHP=1/2/3
ESTIMATE TTEMP=7S.0,CTEMP=7S.0,BTEMP=100,RTEMP=100

VERSION 0404
SIMULATION SCIENCES, INC.
PROJECT FVO
PROBLEM MSK PURIF.

SM
PROCESS
UNIT 1 - ACOl
SOlUTION

I SUHMARY FOR COLUMN

UNIT

P~GE

A,

AND H

FE.JJ7

1 - ACOL"

1 TOT Al Nut1BER OF ITERATIONS

FAST METHOD
SURE !1ETHOD

o
7

2 cOlurm SUMMARY
TRAY

TEMP
DEG C

1.

3
4

5
6

7
8
9

10
11
12
13
14
15
1.6
11
18
19
20
3

18.3
79.5
80.1
80.6
81.1
81.7
82.3
82.7
83.0
83.3
83.6
83.9
84.2
84.5
84.8
85.1
85.4
85.8
66.5
81.7

PRESSURE
BAR
1.00
1.01
1.02
1.03
1.04
1.05
1.06
1.07
1.08
1.09
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.1.1
1.18
1.19

NET
LIQUID
PHASE(L)

RATES, KG MOLS/Ha
HEAT (COOL) ER
VAPOR
DUTIES
PHASE(V}
FEED
PRODUCT MM KJ /HH

FLO~

59.7
59.7
59.5
59.3
59.1
58.9 ) /
131.7 .
1.31.8
131.9
132.1
132.2
132.3
132.4
132.5
132.5
132.5
132.5
132~3

131.8

92.1
92.1
92.0
91.8
91.6
91.3
92.1
92.2
92.3
92.5
92.6
92.7
92.8
92.8
92.9
92.9
92.9
92.7
92.2

32.5L

-3.0000

39.6L

3.0331

72.1L

FEED Arm PRCDUCT STREAMS

* FEED STREAMS:
FD
TO TRAY 7 IS LIQUID
* PRODUCT STREAMS:
ABOT IS lIQUID STREAM FROM TRAY 20
ATOP IS lIQUID STREAM FROM TRAY 1
OVERALL HASS BAlANCE, (FEEDS - PRCDS)
OVERALL HEAT BALANCE" (HIN - HOUT)

MASS RATES
KG MOlS/HR

HEAT RAIES

0.72070E+02

0.91590E+00

0.39603E+02
0.32467E+02

o .58 0 7 9E +00

MM KJ

0.37439E+00

O.OOOOOE+OO
-0.62237E-02

4 SPECIFICATION VAlUES

PARA!1ETER TRAY COMP. SPECIFICATION

TYPE
NO
NO
TYPE
STRM ATOP
1
1
\J.F

:17

/Hf<

SPECIFIED
VALUE
0.9900E+00

CALCULATED
VALUE
0.9896E+00

VERSION 0404
SIMULATION SCIENCES. INC.
PROJECT FVO
PROBLEN MeK PURIF.

SM
PROCESS
UNIT 1 - ACOL
SOLUTION
TRAY COMPOSITIONS

IIA
TRAY
COMPONENT
1 MEK
2 SBUOH
3 YATER
KG t10LS/HR
TRAY
COMPOHENT
1 MEK
2 SBUOB
3 \.lATER
KG HOLS/HR
TRAY
COHPONENT
1 MEK
2 SBUOH
3 WATER
KG HOLS/HR
TRAY
COMPONENT
1 HEK
2 SBUOH
3 WATER
KG MOLS/BR
TRAY
COHPONENT
1 MEK
2 SBUOH
3 WATER
KG

~10LS/HR

TRAY
COMPONENT
1 MEK
2 SBUOH
3 WATER
KG HOLS/HR

--------

PA GI::
9
A.
ANC R.
FEB67

--------

--------

--------

0.98l5E+OO
0.7347E-02
0.11l0E-Ol

Y
O.9615E+OO
O.7347E-02
o .1110E-Ol

o .9626E+00
0.l466E-Ol
0.2763E-02

Y
o .9611E+00
0.7344E-02
O.lllOE-Ol

O.5967E+02

0.3247E+02

o .5966E+02

O.9213E+02

--------

-------

--------

------y .

0.9747E+00
0.2367E-OI
o .1412E-02

Y
O.9617E+OO
O.1209E-Ol
O.5699E-Q2

0.9636E+00
O.3S25E-Ol
o .l19SE-02

O. 9766E +00
O.1603E-01
O.4629E-02

O.59S0E+02

0.92l2E+02

0.5930E+02

0.9l97E+02

--------

0.9497E+00
O.4909E-Ol
o .ll60E-02

------Y
0.9696E+OO
O.2S37E-Ol
0.4697E-02

O.9333E+00
0.6SS8E-Ol
o .llSSE-02

Y
0.9606E+00
O.3429E-Ol
O. 4663E -02

O.S909E+02

0.9l77E+02

o .5666E+02

O. 9lS5E +02

--------

--------

--------

--------

--------

e -------

X
0.9l4IE+OO
O.647lE-Ol
0.ll53E-02

Y
O.9504E+OO
0.4469E-Ol
O.4669E-02

0.9148E+OO
0.6460E-01
o .405lE-03

Y
O.9531E+OO
O.4Sl6E-01
o .1649E-02

0.l317E+03

0.9133E+02

0.l3l6E+03

O. 9207E +02

--------

--------

--------

10

--------

X
0.9l50E+OO
o .6466E-Ol
0.l424E-03

Y
0.9540E+00
0.4534E-Ol
0.579lE-03

0.9l50E+00
0.6493E-Ol
o .SOO7E-04

0.9542E+00
0.4S49E-01
0.2034E-03

0.13l9E+03

O.922lE+02

O.l32lE+03

O.9233E+02

--------

11

--------

Y.

--------

12

--------

0.9l50E+OO
o .6S00E-Ol
O.l763E-04

Y
O.9542E+OO
O.4563E-Ol
O.7l53E-04

X
O.9l49E+OO
o .6Sl0E-Ol
o .621SE-05

Y
o .954lE+00
O.4579E-01
O.2517E-04

o .1322E+03

O.9246E+02

o .1323E+03

0.9257E+02

VERSION 0484
SIHULATION SCIENCES, INC.
PROJECT FVO
PROBLEM MSK PURIF.
TRAY
COMPONENT
1 HEK
2 SDUOH
3 WATER
KG 110lS/HR
TRAY
CDt1PONENT
1 HEK
2 SBUOH
3 WATER
KG

~1OlS/HR

TRAY
COHPONEN!
1 HEK
2 SBUOH
3 WATER
KG HOlS/HR
TRAY
COt1PONENT
1 MEK
2 SBUOH
3 ~ATER
KG 110LS/HR

SH
PROCESS
UNIT 1 - ACOl
SOlUIION

--------

13

--------

PAGE 10
A.
AND R
fEB87

--------

--------

14

0.9147E+00
o.8527E-01
0.2193E-05

Y
0.9539E+00
0.4597E-01
O.8870E-05

X
0.9144E+00
0.8559E-01
0.7747E-06

Y
0.9536E+00
0.4624E-Ol
o. 3129E -05

0.1324E+03

0.9267E+02

0.1325E+03

0.9277E+02

--------

15

--------

--------

--------

16

X
0.9137E+00
0.8628E-Ol
0.2739E-06

Y.
0.9531E+00
O.4673E-Ol
O.110SE-05

X
0.9121E+OO
0.8791E-01
o .9682E-07

Y
0.9520E+00
O.477SE-Ol
0.3900E-06

0.1325E+03

0.9285E+02

0.1325E+03

O. 9291E+ 02

-_._ -----

--------

-------- 17 ------X
Y
0.9082E+00 0.9497E+00
0.9185E-01 o .5009E-01
0.3416E-07 0.1375E-06

X
O.8986E+00
o .1014E+00
0.1196E-07

0.9440E+00
0.5569E-Ol
0.4816E-07

0.9294E+02

0.1323E+03

0.9288E+02

0.1325E+03

--------

19

--------

18

--------

20

--------

0.8758E+00
o .1242E+00
o .40 84E-08

Y
0.9307E+00
0.6924E-01
o .1651E-07

X
0.8234E+00
o .1766E+00
o .1293E-08

Y
O. 8989E +00
o .1017E +00
0.5285E-08

0.1318E+03

0.9269E+02

0.3960E+02

0.9216E+02

VERS ION 0484

SIMULATION SCIENCES, INC.
PROJECT FVO
PROBLEH HEK PURIF.

PROCESS

SH
PAGE
Al .

SOLUIION

FEB67

STREAH SUMMARY
STREAH ID.
NAHE
PHASE
FROM UNIT/TRAY
Ta UNIT/TRA Y
FROM STREAt1
KG MOlS/HR
I~1PERATURE,

DEG C

PRESSURE, BAR
H, MM KJ /HR
H KJ /KG MOlE
KJ /KG
MOlE FRACT LIQUIO

11 KGS/HR
MOLECULAR ~EIGHT
STO LIQ
IB/HR
OEG API
SP GR
KGS/l-!3
UOP K
REOUCEO TEMP
REOUCED PRESS
ACENIRIC FACTOR
*:::VAPOR**
M KGS/HR
t10lECULAP. \JEIGHT
STO LIQ
M3/HR
STO M M3/HR
ACIUAL H H3/HR

ATOP

LIQUID
Ol 0
11 7

LIQUID

:IQUID

72.070
60.413
1.060
0.916
12.706
176.409
1.00000

39.603
87.652
1.190
0.581
14.665
202.361
1.00000

32.467
76.313
1.000
0.374
11.532
1G1.231
1.00000

5.192
72.040
6.423
43.193
0.6100
806.3293
10.632
0.659
0.025
0.350

2.670
72.464
3.551
43.231
0.6096
806.1536
10.649
0.674
0.029
0.369

2.322
71.522
2.672
'D.145
0.6102
808.5463
10.611
0.655
0.023
0.326

0.000
0.000
0.000
0.000
0.000
0.000
0.00000

0.000
0.000
0.000
0.000
0.000
0.000
0.00000

0.000
0.000
0.000
0.000
0.000
0.000
0.00000

1/ 20
Ol 0

1/
0/

1
0

113

/KG MOL

O.OOOOE+OO

O.OOOOE+OO

O.OOOOE+OO

5.192
72.040
6.423
37.3663
6.487
611.761
0.00425
1.7423E+02

2.670
72.464
3.551
20.7729
4.716
606.261
0.00473
1.7913E+02

2.322
71.522
2.872
16.7752
3.610
609.462
0.00402
1.6861E+02

::::::~IQUID**

t1 KGS/BR
MOLECULAR \JEIGHT
STO LIQ
M3/HR
ACTUAL GPl1
H3/HR
KGS/H3

CP,KJ

ABOT

KGS/H

CP,KJ

FO

/KG Mal

/00

At~D

17
Fr

----- ._.--_ .--

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

A-7

Strea m data MEK puri ficat ion colum n T5l

VERSION 0484

PROCESS

SM

INPUT LISTING - PAGE

GENERAL DATA
TITLE USER=A
AND R
,PROBLEM=MEK PURIF.,PROJECT=FVO,DATE=FED87
OlMEN SION S1,TEMP=C,PRESS=BAR
PRINT WTOPTION
COMPONENT DATA
L1BIO 1,MEK/2,SBUOH
THERMOOYNAMIC DATA
TYPE SYSTEM=SRK
STREAM DATA
PROPERTY STRM=FD,PRESS=1.0,PHASE=L,~
COMP(M)=1,82.338/2,~7.662,NOCHECK,RA

TE(M)=39

.6032
UNIT OPERATIONS
COLUMN UID=BCOL,KPR1NT
PARAMETER TRAY=25,FAST=5,SURE=30,DKDX
FEED FD,7
_PRO DUCT OVHD=ATOP, 32.6 085, BTMS =ABOT , 6 .99" 7
HEATER 1,25 ,3/2 ,1,-4 .0
CONDENSER TYPE=3,PRESSURE=1.0
PSPEC TOP= 1.01, DP=0 .Ol
SPEC STRM=ABOT,COMP=2,2,FRACTION(W) =0.99
VARIABLE HEAT=l
PRINT TRAY=25
PLOT PROFILC,XCOMP=1/2,YCOMP=1/2
ESIINATE ITEMP=75.0,CTEMP=75.0,BTEMP=100,RTEMP=100

lOl

VERSION 0484
SIMULATION SCIENCES, INC.
PROJECT FVO
PROBLEM MEK PURIF.

SM
PROCESS
UNIT 1 - BCOL
SOLUTION

I SUMMARY FOR COLUMN

UNIT

1 -

PAGE
8
AND R

FEB87

BCOL,

1 TOTAL NUMBER OF ITERATIONS

FAST HETHOO
SURE METHOO

o
4

COLUMN SUMMARY

TRAY

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
3

TEMP

PRESSURE

DEG C

BAR

79.4
79.8
80.3
80.8
81.4
82.1
82.9
83.2
83.6
84.1
84.6
85.4
86.4
87.9
89.9
92.3
95.0
97.5
99.7
101.4
102.6
103.5
104.2
104.7
105.1

1.00
1.01
1.02
1.03
1.04
1.05
1.06
1.07
1.08
1.09
1.10
1.11
1.12
1.13
1.14
1.15
1.16
1.17
1.18
1.19
1.20
1.21
1.22
1.23
1.24

NET FLOU RATES, KG MOLS/HR

HEAT(COOL)ER
LIQUIO
VAPOR
DUTIES
PHASE(L) PHASE(V)
FEED
pnODUCT MM KJ IHR
90.6
90.4
90.2
89.9
89.5
89.0
128.9
128.9
128.8
128.6
128.2
127.4
126.2
124.4
122.0
119.~

116.9
114.8
113.3
112.3
111.7
111.3
111.1
111.0

123.4 '
123.2
123.0
122.7
122.3
121.7
122.1
122.1
122.0
121.8
121.3
120.6
119.4
117.5
115.2
112.5
110.0
108.0
106.5
105.5
104.8
104.5
104.3
104.2

FE EO AND PRODUCT STREAMS

* FEED STREAMS:
FD
TO TRAY 7 IS LIQUID
* PRODUCT STREAMS:
ABOT IS LIQUIO STREAM FROM TRAY 25
ATOP IS LIQUIO STREAM FROM IRAY 1
OVERALL MASS BALANCE, (FEEOS - PROOS)
OVERALL HEAT BALANCE, (HIN - HOUI)

10'2..

32.8L

-4.0000

6.8L

4.0153

39.6L

MASS RAIES
KG MOLS/HR

HEAT RATES
MM KJ IHR

0.39603E+02

0.54223E+00

0.68389E+01
0.32764E+02

o .17689E+00
o .3B061E+OO

O.OOOOOE+OO
0.15914E-04

VERSION 0484
SIMULATION SCIENCES, INC.
PROJECT FVO
PROBLEH MEK PURIF.

SM
PROCESS
UNIT 1 - BCOL
SOLUTION
TRAY COMPOSITIONS

IIA
TRAY
COHPONENT
1 MEK
2 SBUOH
KG MOLS/HR
TRAY
COMPONENT
1 MEK
2 SBUOH
KG MOLS/HR
TRAY
COHPONENT
1 MEK
2 SBUOH
KG HOLS/HH
TRAY
COHPONENT
1 MEK
2 SBUOH
KG MOLS/HH
TRAY
COt1PONENT
1 MEK
2 SBUOH
KG MOLS/HR
TRAY
COMPONENT
1 MEK
2 SBUOH
KG MOLS/HR
TRAY
COMPONENT
1 MEK
2 SBUOH
KG MOLS/HR

--------

PAGE 10
A.
AND R
FEB87

--------

--------

--------

0.9931E+OO
0.6903E-02

Y
0.9931E+00
0.6903E-02

X
0.9864E+00
0.1365E-01

Y
0.9931E+00
0.6903E-02

0.9059E+02

0.3276E+02

o .9045E+02

0.1234E+03

--------

0.9767E+OO
O.2326E-01

------Y
0.9881E+00
O.1185E-01

o.9633E+OO
0.3673E-01

-------Y
O.9811E+OO
O.1890E-01

O.9023E+02

O.1232E+03

0.8993E+02

0.1230E+03

--------

0.9448E+00
0.5518E-01

------Y
0.9712E+00
o.2876E-01

X
0.9202E+OO
0.1915E-01

Y
O. 9578E +00
0.4225E-01

0.8951E+02

O.1221E+03

0.8896E+02

0.1223E+03

--------

--------

--------

--------

--------

--------

--------

O.8887E+OO
0.1113E+00

Y
O.9399E+00
0.6015E-01

0.8856E+OO
o.1144E+OO

Y
O.9379E+OO
0.6207E-01

0.1289E+03

0.12l1E+03

0.l289E+03

0.l22lE+03

--------

X
0.8802E+00
0.1l98E+OO

------Y
0.93Q7E+00
0.6535E-01

X
0.8101E+00
0.l293E+00

-------Y
0.9290E+OO
o.1l05E-01

0.l288E+03

0.l22lE+03

o.l286E+03

o.1220E +03

--------

--------

-------

11

--------

10

12

--------

0.8543E+00
0.1457E+OO

Y
0.9l90E+00
O.8097E-Ol

0.8261E+00
o .l133E+00

Y
0.9019E+OO
0.98l0E-Ol

0.l282E+03

o.l2l8E+03

0.l27QE+03

0.12l3E+03

--------

-------

13

--------

14

-------Y
O.8260E+OO
O.1140E+OO

O.7818E+00
0.2182E+OO

Y
0.8130E+00
o.1210E+00

X
0.7l36E+OO
o.2864E+OO

0.1262E+03

o.1206E+03

o .l2Q4E+03 o .1194E+03

103

VERSION 0484
SIMULATION SCIENCES. INC.
PROJECT FVO
PROBLEH HEK PURIF.
TRAY
COMPONEN::
1 MEK
2 SBUOH
KG HOLS/HR
TRAY
COHPONENT
1 MEK
2 SBUOH
KG .HOLS/HR
TRAY
CQt'1PONENT
1 MEK
2 SBUOH
KG

~mLS/HR

TRAY
COHPONENT
1 MEK
2 5BUOH
KG l10LS/HR
TRAY
COMPONENT
1 MEK
2 5BUOH
KG MOL5/HR
TRAY
COMPONENT
1 MEK
2 5BUOH
KG MOLS/HR

SM
PROCESS
UNIT 1 - BCOL
SOLUTION

-------- 1S

--------

PAGE 11
AND R
FEB87
A

--------

--------

16

0.619SE+00
0.380SE+OO

Y
0.7S46E+00
O.24S4E+OO

o .SOSOE+OO
O.49S0E+00

Y
O.6SS7E+OO
O.3443E+OO

0.1220E+03

O.117SE+03

O.1194E+03

o .11S2E+03

-------

-------- 17

-------- 18

--------

O.3843E+00
o .61S7E+OO

Y
O.S3S1E+OO
0.4649E+00

O.2142E+OO
O.72SBE+00

Y
O.407SE+00
O.S924E+OO

0.1169E+03

0.112SE+03

o .1lC~8E+03

O.1100E+03

--------

-------- 19

--------

20

--------

0.18SSE+00
o .814SE+00

Y
0.2909E+OO
0.7091E+00

0.1206E+00
0.8194E+OO

Y
0.1961E+00
o .8032E+00

0.1133E+03

0.1080E+03

o .1123E+03

o .106SE+03

-------- 21

--------

--------

22

--------

0.7622E-01
0.9238E+00

Y
O.1277E+00
0.8723E+OO

O.4125E-01
O.9S27E+OO

Y
O. 80S2E -01
O. 9195E+ 00

0.1117E+03

o .105SE+03

o .1113E+03

0.1048E+03

--------

23

--------

--------

24

--------

o .288SE-01
0.9711E+00

Y
O.4967E-01
0.9S03E+OO

0.1731E-01
0.9826E+00

Y
0.3007E-01
0.9699E+00

0.1111E+03

O.104SE+03

0.1110E+03

O.1043E+03

--------

25

--------

o .l027E-Ol
0.9897E+OO

Y
o .1783E-Ol
O.9822E+00

O.6839E+01

O.10Q2E+03

VERSION 0484
SIMULATION SCIENCES, INC.
PROJECT FVO
PROBLEM MEK PURIF.

SM

PROCESS

PAGE
A. _

SOLUI10N

FEB87

STREAM SUMMARY
STREAH 10.
NAtiE
PHASE
FROM UNIT/TRA Y
TO UNIT/TRAY
FROM STREAM

FO
LIQUIO
1/

39.603
82.184
1.060
0.5'12
13.692
188.94'1
1.00000

6.839
105.093
1.240
0.177
25.865
3"9.041
1.00000

32.76"
79.378
1.000
0.381
11.617
161.068
1.00000

2.870
72.464
3.551
"3.231
0.8098
808.1538
10.6'19
0.663
0.025
0.369

0.507
74.103
0.627
"3.195
0.8100
.808.3179
10.805
0.706
0.030
0.576

2.363
72.122
2.92"
tB.238
0.8098
800.1187
10.616
0.658
0.024
0.326

0.000
0.000
0.000
0.000
0.000
0.000
0.00000

0.000
0.000
0.000
0.000
0.000
0.000
0.00000

O.OOOOE+OO

0.000
0.000
0.000
0.000
0.000
0.000
0.00000

O.OOOOE+OO

O.OOOOE+OO

2.870
72."64
3.551
20.5947
".678
613.525
0.00424
1.7730E+02

0.507
74.103
0.627
3.56"0
0.809
626.063
0.00467
2.1822E+02

2.363
72.122
2.92"
17.0973
3.883
608.521
0.0040"
1.7023E+02

M KGS/HR
MOLECULAR WEIGHI
STO LIQ
M3/HR
OEG API
SP GR
KGS/M3
UOP K
REDUCEO IEMP
REDUCEO PRESS
ACENIRIC FACTOR
**VAPOR**
M KGS/HR
MOLECULAR WEIGHT
SlO L1Q
H3/HR
SlO M M3/HR
ACIUAL M M3/HR
KGS/M
M3
Z
*::rLIQUIO~

M KGS/HR
MOLECULAR WEIGHT
SlO LIQ
M3/HR
ACIUAL GPM
M3/HR
KGS/M3
Z

CP,KJ

/KG MOL

LIQUIO

1/ 25
0/ 0

/KG

/KG MOL

LIQUID

MOLE FRACT LIQUID

CP,KJ

ATOP

0/

KG l-tOLS/HR
rEMPERATURE. DEG C
PRESSURE, BAR
H, MM KJ /HR
M KJ /KG MOLE
KJ

ABOT

/05

1/
0/

1
0

22

AND R'

A-8

Utility costs

It is assumed that utility costs exists of cooling water, steam,

electricity and natural gas costs.
Cooling water:

Available at a temperature of 20C.

Maximum allowed temperature 40C.
Costs: f 0.06/m 3

Steam:

Available at 190C and 3 bar. Enthalpy change

when condensed to water (100C and 1 bar) is
2365.4 kJ/kg. Costs:

40.-/ton.

Electricity:

Costs: f 0.19/kWh.

Natural gas:

Lower heating value 37.68 MJ/kg.

Costs:

f 14.40/GJ.

Table (1): Cooling water demand

Equipment

Capacity

no.

kW

C.w. rate
m3 /hr

H2

489

21. 064

T3

5416

232.992

H4

506

21. 758

H18

1889

81. 281

H27

",2700

116.172

H32

220

9.464

H38

302

12.974

H40

21

0.891

H47

832

35.777

H55

1123

48.312

H57

59

2.556

H58

57

2.448

Total

585.689
3

Total annual cooling water costs: f 253,018

/0

Table (2): Steam demand

Equipment

Capacity

Steam rate

no.

kW

ton/hr

H13

1.987

1305

T14

2.952

H19

0.041

H24

27
",1500

2.283

H30

",1200

1. 825

H44

843

1. 282

H52

1115

1. 697

Total

12.067

Total annual steam costs:

f 3,475,296

For

only compressor Cl is taken in acount.

electricity

demand

The power demand of 105.3 kW requires annual f 144,050.

For

the

demand of natural gas two cases have been regarded:

in

case 1 the acid-reconcentration unit is fully supported by hot flue

gases

(no

natural

gas demand) while in case 2 this unit is fully

supported by natural gas combustion.

Table (3): Natural gas demand
Equipment

Capacity

no.

kW

kg/hr

F36

225

21. 50

R37

668

63.82

Total case 1
acid-reconc.

Gas flow rate

85.32
9736

930.20

Total case 2

1015.52

Total gas casts: case 1 : f

333,310
Total gas casts: case 2: f 3,967,253
The total annual utility casts for case 1 : f

4,205,674

The total annual utility casts for case 2: f

7,839,617

In
10%

the

used

economic model the utility casts are estimated as

of the total production casts of f 51,835,530/yr. This estima-

tion can only be justified wh en at least 73% of the required energy

for acid reconcentration is supplied by flue gases.

/o~

R _ G. .

D;~

T23

:-: re

: 1"'116

1-

:----~::J

:~~oy~,

to Sewer

St m

I
:::ftl:

nc ... '

H19

Hydrogen

Ing Wat.,.

H32

V33

[!!~
F ....'

C , GAS COMPRESSOfI
H 2 CONDENSOR
T 3 8UTENE A8SOReER

H 4 AC/O COOLER
P!I AC/O ~
11 8
C)o1
11 8
11 11
PlO
.. "

RECONCEHTRAT1ON IIUSEl
GAS-UOUO SE_OR
RECONCENTRATIOH IlESSEl
HYDAOLYSIS TANK
ACID PUMP
IlENTUIII SCR~R

HUnR
Sec. 8UTANOI. STRIPPER
PUMP
STOIIAGE
CAUSTIC SCRU8eER

CONlEHSOR

PREHUTER
l'O. -l'O. SE""'RATOR .
~

T 23
H24
P2!1
1128
H21
P28

OISTUATIQH C~

REIIOIl.ER
REFlUX PUMP
UO. l/O. SEP""'ATOR
COI;OENSOR

PUMP
Uil OISTUATIOH CCU~

~~~ER
H32 COOLER
1133 AlCOHol. SlORAGE

Pl~

Hl!l
F3e
Rl7
Hle
C)o
H~
H"'
P42
Hl
H~~

PUMP
HEAT EXCHANGER
FUANACE
MUlT' TUBUlAR REACTOR
CONDENSOR
GASllOiAO SEPARATQII
CONDENSOR
O)NDf.N!iOII
~

O'STIL'. AT'ON COLUMN

RE8ou. ER

VESSEL
P", RE
FL UX PUMP
CONDENSOR

v~e

~7

PUMP
P"II PUMP
P~
REC'lClE
T~l DlSTIllATtON CQl.1"II.4N
H!l2 RE80ILER
P~l REFl.UX PUMP
V~ lIESSEL
H!I CONDENSOR

P~8

PUMP

PROCESS SCHEME FOR PROOUCnoN

OF METHYL ETHYL KETONE
F: V O. no. 2e8J
April 1~81

A .H. Amer
R .F" . de Ruiter

OStreom na.
P!III PUMP
H~7 COOLER
H
COOLER

[IJ ~ In -C

@Pr.....

In

ar

~Yltem~

nol gI .... Is' 80r

Errata

on flow sheet F.V.O. no. 2693:

1
2
3
4

To prevent an inert-build up in T3, a part of stream 7 must be

purged.
Butene absorber T3 is not a jacketed vessel but a vessel with
multitubular internal cooling.
Gas-liquid separators Cy7 and Cy39 are not cyclones but
horizontal separation tanks.
NaOH for acid removal can be exchanged with Ca(OH)z, which is
+

5
6

cheaper. CaS04 removal is easier than Na /SO~

removal.
Brine-cooling for but ene liquification is only necessary when
normal cooling water is not able to reduce the temperature to
25C.
Liquid-liquid separator V20 is a horizontal vessel.

,//