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FluidPhase~qquilibria,40 (1988) 113-125

Elsevier Science Publishers B.V., Amsterdam Printed in The Netherlands

113

VAPOR PRESSURESOF N-BUTANE,DIMETHYLETHER, METHYL CHLORIDE,METHANOL AND THE VAPOR-LIPUID EQUILIBRIUM DIMETHYLETHER - METHANOL: OF EXPERIMENTAL APPARATUS,RESULTS AND DATA REDUCTIDN

H. HOLLOORFFand H. KNAPP Institute Thermodynamics of and Plant Design, TechnicalUniversityBerlin (F.R.G.1
(Received July 27, 198’ accepted in final form November 30, 1987) 7;

ABSTRACT

Holldorff, H. andKnapp, 1988. H., Vapor pressures of n-butane, dimethyl ether, methyl chloride, methanol and the vapor-liquid equilibrium of dimethyl ether-methanol; experimental apparatus, results and data reduction. Fluid Phase Equilibria, 40: 113-125.

A static equilibrium apparatus for experimental investigations of vaporliquid and vapor-liquid-liquid phase equilibria pressures 10 kPa < p < 1 MPa at and temperatures 250 K < T < 350 K was designedand built. The vapor pressureof n-butane
was measured at 258 K < T < 357 K in order to

test the the operability and accuracyof the entire system. Vapor pressures of dimethyl ether, methyl chloride and methanol were measured;Vapor-liquid equilibriain the binary mixture of dimethyl ether and methanolwere investigated. The experimental resultswere reduced.

INTRODUCTION The design, selection,or optimization of separationprocesses in chemical production plants requiresinformation on phase equilibria.In many cases It
knowledge in molecular theory

1s
and

not possible to predict the conditionsin multicomponent and multiphase with sufficient accuracyand certainty. Our
our

systems

models of liquid solutionsare still imperfect particularly for strongly
polar or

interacting, highly

assoclatlng molecules.

The required informatlon must be obtained in the experiment.Experimental data are costly and only sporadic
design but are of theory. essential for responsible process

and for further improvement

037%3812/88/$03.50

0 1988 Elsevier Science Publishers

B.W.

114

This report is the first of a seriesof reports on results of an experimental study of phase equilibria of mixturescontainingCHJOCH3, (see Table 1). These components can waste water treatment. TABLE 1 Experimental program Substance 1 2 %"bO CH,Cl CH,OH %"6O CH,OH pLv/kPa min max 128 124 13 35 1073 1098 243 1078 TLV/K min max 254 25& 293 2% 321 322 362 353 Pts
be found for example,
CH,Cl, CH>OH

and HZ0

in plants producing

methyl ceilulose and must be separatedfor varies reasons, such as recoveryand

19 29 15 72

EXPERIMENTAL METHOD At high vapor pressures, with components very differentvolatilities, of in the presence of two liquidphases it is difficultto take representative liquid samplesfor chemicalanalysis. It is advantaqous to use a static cell and or The static method is one prepare the mixture gravimetrically volumetrically. of the oldest methods used to study phase equilibria(Magnus 1836). Recent years have shown an increasinq interestin this method, and a variety of apparatuses have been describedin
literature (e.g.

Van Ness and Gibbs 1972, Pembertonand

Mash 1978, Aim 1978, Kolbe

and Gmehling 1985).

EXPERIMENTAL EQUIPMENT The

cell is shown in figure static equilibrium
The

1.

It

is

designed for maximum
(9 nnn) Doran glass by

pressuresof 1.5 MPa.
cylinder stainless (4).
The

cell is

made of

a thick-walled

(H = 100 mm, Di = 81 mn. V = 512 cm') (1)
steel
cell is

closed on both sides
Teflon as

(W 1.4571)
filled 9/10

cover-plates
with liquid.

(2,

3)

with

gasket material
is still a

Corrections the liquid composition of
minimal. However there

due to

partial

vaporization large

are therefore

vapor inventory

enough to allow withdrawalof samples without affecting

pressureand composition.
An excentric
and distributes

hollow-shaft
them near

stirrer
the

(5)

sucks

vapor

and liquid shaft is

from the surface sealed by a teflon

bottom.

The stirrer

packing

(6)

and mercury

(7)

and is driven

by an electric

motor at 200 min

-1

.

115

Fig.

1. Equilibrium The Liquid

cell injected septa into (8). the cell through capillaries, sensor which

components are (9).

are inserted

through teflon-coated

The temperature

1s inserted

in a therm0 well The complete The glass containrng by a range of interspace volatile

system is shown schematrcally cell (1) (3) is

in Figure

2. wall glass vessel (2) K

equilibrium

immersed in a double temperature F3-k). be viewed to prevent degassed

40 1 of a water-glycol thermostat purged with Different 250 K < T < 360 K. The 1s liquids

mixture, (Haake cell can

controlled through fogging

within

~0.02

circulation

The thermostat at

has an operating a window (4). low into the cell: The low from operating

dry nitrogen

temperatures.

methods are

used to fill carefully

substances

(HzO, CH,OH) are

and then transferred

116

Fig.

2.

Schematic
flasks (6)

diagram
by

of

the

static
type

phase

equilrbrium
pumps

apparatus.
(5).

storage

diaphragm

dosrmetric

High flasks caprllaries

volatile (7) into (81, The

substances

(CZH6U,

CH,Cl)

are

distilled samples (VI and
can

From the high
be withdrawn

pressure
through

the refrrgerated evaporated entire in

cell. needle

Liquid valves

collected

as

vapor

in sample

flasks.

system

can be evacuated and control in the (101 was in

by a vacuum pump (15).

Instrumentation

The temperatures temperature 51223). The sensors system 162 CE). is

bath

and

equilibrium with

cell

are measured indicator resistance

by PtlOO

combination against

a digrtal

(Systemteknik thermometer

calrbrated

a standard

(Rosemount The cell Baldwin
9B°C to

connected (11)

to one side whrch is

of

a differential directly
the

pressure above
inductive

gauge

(Hdttxrger
to

PDl/O.l)
prevent

located

the cell is

and heated adjust pressure

condensation

and to

thermostat

PD-transmitter. used to

The the is

differential reference
read

pressure pressure

indicator-controller
or venting

c&p 210 kPa)
nitrogen

by adding

(121. (13)

The reference (Wallace

on an aneroid

precision balance
component

pressure (14)
filled

indicator

& Tiernan

61-1500)

or set

by a pressure
each scale

(Oesgranqes
into the

6 Huot 3030-Zl-PR).
cell is

The mass of on a precls~on

determined
flasks

gravrmetrically
(6 and 7) before

(m 21 mg) by weighing

the storage

117 and after correcting filling. for The composrtion contained can be of the liquid in the vapor determined conductivity by phase fraction. a gaschromatograph calibrated with (Hewlett reference can be calculated after

the portlon composition A) with

The vapor Packard mixtures.
Table 2

5830

a thermal

detector

lists

the

sensitivity resulting

of

the

instruments

or

systems
handling,

and

their
etc..

estimated TABLE 2 Sensitivity Variable

inaccuracy,

from calibration,

fluctuation,

and inaccuracy Instrument

of

the instrumentation Sensitivity Inaccuracy

or Method

T (K) Ap (kPa1 p (kPal p (kPa) x (mol/molj y (mol/mol) * dependent

resistance
differential

thermometer pressure manometer balance gauge

0.01 0.01 0.02 0.01: 0.00001 0.00001 range

0.04 0.05 0.06 0.1% 0.0001 0.003~0.01’

aneroid pressure

gravimetrical gaschromatograph on component and concentration

SUBSTANCES The water Merck with The inert vacuum for Dimethyl chloride used is a purity gases 15-30 ether were deionised of min.
removed

and

double

distilled.

Methanol

was supplied less

by

99.5% and a maximum water content
from both

than 0.01%. under

liqurds

by partial

evaporatian

minutes. and methyl no measurable chloride were in N2. provided by Henkel KGaA. Methyl on

showed

impurities except

gaschromatographic It was degassed

analysis by

Porapak Q and freezing, Several of the procedure estimated

Carbowax 1540 columns the gas phase, mainly They as used

repeated

evacuating impurities.

and thawing. by gaschromatographic distlllatlon. The final The analysis degasslng was

COz, were detected were for removed methyl
by

dimethyl was

ether. the same

chloride.

purity

to be 99.8%. was chosen
the purity

N-butane
specifications,

as

a

test

substance. than 99.95%

According

to

the

suppliers

was better

118

EXPERIMENTAL

RESULTS

Test

measurement

The vapor of the in 5.

pressure system 3. The

curve and

of the

n-butane accuracy and

was measured, of the

to

check

the

functioning are in

complete Table The

instrumentation. parameters

The results are presented

shown Table well

Antoine of to the

Frost-Kalkwarf

scattering deviations

experimental

points

can

be seen

in

Figure

3,

as

as

the

vapor

pressure

equations

recommended

by other

authors.

s

0.60

255

270

280

290

300

320 T . K

340

360

temperature
fig. 3. 1977; 21 of Relative authors 0 n-butane. pressure (OHaynes et deviation al., 1973) of

measured 1982;v to

data the

l

and et

calculated al., 1982;O pressure

values Reid correlation

af et

different al., (Eq.

and Goodwin,

Kratzke

Boublik

compared

vapor

TABLE 3

Vapor

pressure

data

of

n-Butane

T (K)
258.74 268.07 277.90 277.91 297.05 307.57 312.09

p

CkPa) 57.05 84.89 123.AY 123.62 241.86 323.78 372.30

T (K) 312.51 317.51 322.46 322.46 327.56 327.60 332.36

p CkPa) 372.51 427.07 488.07 487.61 556.01 556.58 626.83

1 (K) 337.23 302.31 3A7.24 3A7.25 352.90 356.97

p CkPa) 704.89 793.79 888.17 888. rr6 1006.95 1098.55

119
Vapor pressure of the cure

components
of methyl vapor pressure and measurements methanol. of The the data pure were

Table
components correlated,

4

shows

the

results ether,

dimethyl
~~UWJ the

chloride.

Antoine-Equation

In

(pLv/kPa)

= A - R /

((T/K)-C)

(1)

and

the

Frost-Kalkwarf-Equation

In

(pLv/Torr)

= A + B /
of

(T/K)

+ C ln(T/K)

+ D (p/Torr)

/

(T’ ) /K’

(2) deviation ether, between methyl

The coefflclents experimental chloride,

both

equations points

as well are

as

the

standard dimethyl

and

correlated in

presented

Far

and methanol

Table af the

5.

Vapor-liquid-equilibrium

system dimethyl
to measure

ether

- methanol

It seemed
temperature for

to be

most

practical

vapor

pressures

as a Function

of

mixtures

of

constant points. and or

composition. It is

Vapor samples

were drawn and VI-E-data In an the

analysed

at some equilibrium applications isobaric

advantaqous VLE-data data sets

to have lsabaric For data were reduction. derived

in industrial lteratlve

isothermal
isothermal

procedure

From

experimental Due to
the effect

equilibrium the inventory
of samples

points. of the high volatile
companent in the vapor phase and ,

drawn from the vapor phase,
up to 5.10-’ mol/mol from

the liquid the total

composition composition zi

x

is

not
Table

constant,
6).

but varies

(see

x

V = 2, + - (2, i ALA = molar

-

YJ

(3)

(V/l.

vapor-liquid vapor
Raoult

ratlo) composition in a First vapor yi was not determined approximation
and

Whenever the
estimated iteration with

experimentally,
corrected in a

it

was

second

with second yi

calculated step to

compositions

resulting
vapor

from a consistency
pressures p
LW

test. and vapor original

In a composition

corrections account for

were made on the the small

deviatlans canstant

between ki of

the

experimental

liquid

composition

xi and the defined

the isostere.

120 TABLE 4 Vapor pressure data of dimethyl ether, methyl Methy T (K) 253.81 254.46 254.47 259.24 259.26 259.26 263.12 264.04 264.05 260.79 272.94 274.83 278.90 202.70 203.97 283.97 288.82 292.72 293.94 298.53 302.62 303.44 307.36 312.60 313.28 318.40 318.95 321.44 322.27 Chloride p (kPa) 124.46 127.88 127.80 155.04 154.99 155.24 180.x 106.77 186.53 222.52 250.35 275.12 316.67 359.80 374.20 374.27 435.98 091.12 509.72 583.11 654.70 670.47 746.76 858.58 874.29 995.93 1009.81 1075.36 1097.91 chloride, and methanol Methanol T (K: p (kPa) 292.88 297.75 302.30 307.82 312.81 317.77 322.57 327.75 332.52 337.40 342.62 347.25 351.24 356.97 361.71 12.84 16.54 21.18 27.44 34.96 43.70 54.29 67.56 82.54 lUO.39 122.90 146.07 169.34 207.19 243.37

Dimethyl Ether p (kPa) T (K)

253.85
258.63
258.64 261.08 261.08 265.41 268.25 273.22 278.00 287.94 292.93 297.60 302.93 303.01 307.57 312.95 317.62 320.40 320.51

128.07 155.49 155.59 171.07 171.17 201.98 224.34 267.41 315.19 434.55 506.08 580.96 675.74 677.34 767.74 885.28 997.92 1069.90 1072.80

TABLE 5 Coefficients Substance n-Butane for vapor pressure Equatron 1) 2) Dimethyl Ether 1) 2) Methyl Chloride 1) 2) Methanol 1) 2) A 13.8975 52.4421 14.2457 55.2509 14.2817 47.6175 16.6228 29.2651 equations 9 2267.06 -4232.12 2142.93 -4076.99 2166.95 -3790.56 3657.61 -5020.56 C 28.306 -5.40579 25.678 -5.84553 24.680 -4.66670 32.976 -1.32992 -2.9242 1.7298 2.3335 3.1513 D U(dP/P)(L> 0.0012 0.0005 0.078 0.047 0.063 0.049 0.197 0.182

121 TABLE 6 Experimental VLE data for the system dimethyl x Y ether - methanol

P (kPa) 254.36 263.75 272.90 202 .a3 292.78 302.71 312.64 322.65 332.55 342.30 352.15

(mol/mol~(mol/mol)
0.1229 253.52 253.54 257.40 263.'90 268.72 273.48 283.4'2 288.56 288.76 278.34 303.50 308.38 313.12 323.27 320.36 338.30 343.12 352.68 65.21 65.34

35.17 50.34 67.54 96.44 130.911 175.08 228.82 275.56 376.54 474.07 590.84

0.1228
0.1226 0.1227 0.1227 0.1226 0.1226 0.1226 0.1226 0.1226 0.1227

254.21 258.57 263.94 260.56 273.75 283.42 288.59 273.41 278.31 303.41 303.46 308.26 313.13 323.49 333.25 336.46

70.73 106.94 131.30 154.64 185.32 253.28 295.83 341.57 391.50 450.9e

449.97 511.30 580.22
744.71 930.61 lW2.04

0.4850 0.48Ji 0.4848 0.4837 0.4045 0.4El43 0.11635 0.4EYl 0.4835 0.4839 0.4830 0.4834 0.4837 0.4835 0.4835 0.4834

0.971
0.789 0.787 0.985 0.983 0.776 0.772 0.968 0.963 0.959 0.957 0.953 0.947 0.737 a.921 0.712

81.41 96.77 114.19 135.07 185.09 217.20 217.24 286.13 330.16 374.07 423.16 539.78 608.09 757.10 840.30
1022.70

0.2865 0.985 II.2868 0.965 0.2048 0.781 0.2862 0.978 0.2840 0.975 0.2859 0.971 0.2848 0.962 0.2857 0.756 0.2843 0.956 0.2847 0.743 0.2854 0.935 0.2847 0.925 0.2852 0.920 0.2887 0.884 0.2851 0.866 0.2847 0.2851 0.834 0.2852 0.7543 0.7544 0.7531 0.991 0.7542 0.7540 0.992 0.7530 0.991 0.7536 0.989 0.7528 0.787 0.7534 0.986 0.7526 0.983 0.753ll 0.982 0.7523 0.978 0.7526 0.975 0.7520 0.7519 0.7521 0.969 0.7517 0.958 0.7517 0.7514 0.948

254.23 254.94 259.36 263.61 268.28 268.74 273.66 270.36 283.53

280.67
254.18 263.50 273.06 282.93 272.77 302.71 312.66 322.73 117.62 169.81 240.10 333.70 452.44 602.35 707.16 1014.06 0.8717 0.8719 0.8718 0.8718 0.8717 0.8717 0.8716 0.8716 293.54 298..35 303.57 308.23 313.18 313.39 318.23 323.25 329.06

llO.b3 113.62 134.95 158.30 162.93 191.46 227.93 266.20 315.X 369.33 428.07 490.78 568.70 643.56 132.74 737.15 831.71 940.19 1077.71

TABLE

7 of the consistency test Deviation AADp

Results

Temperature (K)

Deviation AADy (mol/mol)

CkPa) 0.011 0.066 0.027

253.15 273.15 323.15

0.13016 0.0038 0.0112

122

pLvGL) pLv(x:)+ (apLv/aXi)i = (X
Yl$) = Yl(x;) +

1

- x:)

(4)

mpXi),
at constant

(.Ti - xl)
temperature and
the

(5) were calculated the virial Laar model by using foe the Van Laar the with fugacity y I taken

The derivatives
model

for

the activity The

coefficients
in

equation

coefficients.

parameters

Van

were fitted

from the consistency For correlated interand

test. extrapolation, (2). the isosteric vapor vapor pressure data were

by equation of

The corresponding by

compositions

were correlated

as a function

temperature

In y1 = A + El / (T/K)
Fig. In Fig. (with 4

+ C ln(T/K) vapor pressure diagrams curves for for the system T = 253,

(6) CZH60-CHJOH. 293 and 323 K of T-x,y

shows the isosteric 5 examples
of p-x,y

are presented at 293 K).

data for

points

of Chang et al.

11982)

In Fig.

6 examples

diagrams

p = 1, 2 and 5 bars

are shown.

/.

*2l
250

1

I.

I

.

,
290 310 T . K

,
no

,
350

.
370

260

270

tomprature

Vapor pressure Fig. 4. v x1=o.l227, 0 x1=o.2a54,

of dimethyl 0 x1=o.4a39,

mixtures (0 x1=0.000, ether - methanol rxl=0.752a, n x1=0.8718, 0 ~~=~.oooI

380 1000

360
;

aw .

Y c ,; : :

-.

340 -

5.
z i
!j 4.

600

320 -

300 -

400

: 280 -

200

260 -

0 0.0
cngn

a.2
m

0.4
l d

0.6
y, .

0.n
wl/mol c&u

1.0 (11

240 0.0
ccmcmtration xl a-d 7, .

ccocentr.tion x,

molfmol

MQi121

c&Y I11

CH,OCHJ-CH30H

Fig. 5. p-x,y diagram For the system Fig. 6. T-x,y phase diagram the system at l 253.15 K, r293.15 K, CH,OCH,-CH,OH at l 100 kPa, T 200 kPa, n 323.15 K, v data at 293.15 K measured m 500 kPa, the lines are the results by Chang et al.(lY&?),the lines are the OF LegendrepolynomialFits. results of Legendrepolynomialfits

DATA

REDUCTION

Thermodynamic consistency

test

WheneverT,p,x and y were measured a consistency.test can be and was performedas recommended by was represented with a
Fredenslund et al. (1977).

The excess G'ibbs energy

third degree Legendrepolynomial.The required Fugacity

coefficients the vapor phase of
P Vi = exp (

( 2 E Yj Bij - r r Yi Yj Bij 1 ij RT j

1

(71

were calculated with second virial coefficients 8 Hayden and
O’ Connell (1975).

estimatedby the method of 1J

Table 7 lists the average absolute deviations between experimental and calculatedvalues in vapor composition AADy
deviations are practically and in vapor pressure AADp. The

within the experimental inaccuracies.

124 Models for the excess parameters sets, Gibbs energy popular qE-models likelihood were fitted to isothermal

Binary
p,x,y-data The virlal

of several a

applying

maximum

method

(Prausnitz

et al. 19ElO). of the UNIQUAC

coefficients were

were estimated for the

as mentioned model

above.

The parameters for a modified

IJNIQUAC model model,

fitted

original

and also

as suggested

by Prausnitz and

(1980) for alcohols the deviations

and water. are listed in the

The resulting

parameters

irl total pressure model can best

Table

8.

The

Wilson

model and the modified

UNIUUAC

represent

set of data.

TABLE E Results
Model

of

the parameter

estimation
Parameters' A 12 A 21 6(q) (kPa)

Temperature (K)

Margules

253.15 293.15 323.15 253.15 293.15 323.15 253.15 293.15 323.15
253.15 293.15 323.15 253.15 293.15 323.15 253.15 293.15 323.15

1.1437 1.0533 0.9948 0.9150 0.8718 0.8420 -647.74
-789.73

0.2882 0.2210 0.1819 1.5306 1.3322 1.2174 4095.7 4218.0 4362.3
-162.90 -82.258 0.51182 -511.86 -533.90 -542.37 -764.42 -871.65 -945. a2

1.27 3.64 6.79 0.59 1.91 4.19 0.25 0.62 1.69
0.63 1.96 *.22 0.37 1.28 3.16 0.25 0.61 1.75

Van Laar

Wilson

-929.10
3370.9 3322.7 3264.8 2949.2 2979.5 2998.8 4578.0 4682. 4772.2

NRTL

UNIQUAC

Mod.

UNIOIJAC

e

l

UNIplJAC and NRTL parameters in J/mol Third NRTL parameter a = 0.3

SUMMARY A

phase

equilibrium
of VLE and

apparatus

was

designed

and

built range

that

allows

investigations

VLLE in a temperature

and pressure

interesting

for

technical

applications.

125 of dimethyl VLE of authors and the

The n-butane

vapor as

pressure well with of as results the

curves the of binary other

ether,

methyl ether

chloride, - methanol test the

methanol, were

and

dimethyl and

measured. the The excess

Comparison reliability experimental Gibbs energy.

a consrstency of

demonstrated measurements. For the

apparatus were

accuracy

VLE-data

correlated

by several

expressions

Reports methyl

on

further

investrgations and water will

on mixtures follow.

containing

dimethyl

ether,

chloride,

methanol

ACKNOWLEDGEMENTS The authors dustrieller grateful For appreciate the Financial e. support V. in of AIF (Arbeitsgemeinschaft support of our and are Invery

Forschunqsverelnigungen the help of the craftsmen

)
the

for

financial

workshop

lnstltute.

REFERENCES Aim, K., 1978. Fluid Phase Equillbrra, E., 19i3. 2, 119. Pressures of Pure Substances,

Doublik, T., Fried, V., Elsevier, Amsterdam. Chang, E., Calado, J.C.G.,

Hala,

The Vapour

Streett,

W.E.,

1982. P.,

J. 1777.

Chem.

Eng.

Data,

27,

293.

Fredenslund, A., Gmehllnq, usrng UNIFAC, Elsevrer, Hayden,

J., Rassmussen, Amsterdam. J.P., 1975. I.E.C.

Vapor-Liqurd

Cquilibria

J.C.,

O’ Connell,

Proc.

Des.

Dev.

lP,

209.

Haynes, W.M., Goodwrn, R.D., 1982. Thermophysical Properties from 135 to 700 K at Pressures to 70 MPa. National 8ureau Monography 169, Washrngton. Kolbe, Kratzke, Magnus, Pemberton, 8. and Gmehling, H., A., Spillner, 1836. R-C. Ann. J., C., 1985. Muller, Chem. Fluid S., Phase 1982. 38. Chem. Equilrbrla, J. Chem. 23,

of Normal Butane of Standards

213. 14, 1175.

Thermodyn.,

Phys. C.J.,

Poqq., J.

401. Thermodyn., IO, 867. O’ Connell, and Llquidof Gases

and Mash,

1978.

Prausnitz, J.M., Anderson, T.F., Grew, E., Eckert, C., Hsieh, R., J.P., 1980. Computer Calculations For Multlcomponent Vapor-Lrquid Liquid Equilibria. Prentice Hall, Englewood Cliffs, N.J.. Rerd, R.C., Liquids, Van Ness, Prausnltz, McGraw Hill, H.C. J.M., Sherwood, New York. R.E., 1972. T.K., 1977. Ihe

Propertles
Fundam., 11,

and

and Gibbs.

Ind.

Eng.

Cfiem.

3,

010.