Journal 01 Sr ir-nuf.c &. Industrial Research V0J. 68. October 2()()9. pp.

R71-n:,

Entrainer for batch distillation of acetic acid -water

S V Gadek ar '. R v N~ik~and S N Kaulh
'Department
01 Chemical

system

Engineering. Bharati Vidyapceth University College ur EnglJ1eenng. Punr-. India 'Nalional Chemical Laboratory. Pune.Tndia 'National Environmental Engineering Research Institute. lag rUT. India 19 Februarv 2008: revised N June 2009: accepted 21 July 21/0Y

Received

Acetic acid-water sysre m (A W) poses a challc nge in rcactiv e disri llation. acetic acid purity and loss of accnc acid in aqueous solutions. Feasible separation or AW has been studied usin~ emrainer s but acetic acid loss in lean phase cannot he avoided. This study presents feasible rq:ion 10 operate column with toluene and benzene as entruincr for AW. Liquid -Iiqurd equilibrium data and nature of lie line for eihv 1 acetate are given pnoriry.

Introduction
Under batch distillation. of pure components. initial mixture products compositions. to reduce further rccoverv on are highly dependent Use of batch rectifier

feasible separation have been reported". Simulations have been done to find out suitable cnrrainer for AVril. This study presents toluene. benzene and ethyl acetate

and

a~ an entrainer

stripper for hcieroazcotropic systems has gained popularity'. Hillman: studied many process alternatives to achieve Distillation decanter from ideal lean phase. rich phase smoothened Efficiency upon choice Acetic and showed: aqueous to complete conversion distillation of operation. successful for handling systems. Options batch liquid Vapor distillation mixture. -liquid condenses operations. which require differs of heterogeneous

for A \\1 to reduce amount of acetic acid loss in aqueous phase of distillate using Residue Curve Map (ReM).

Experimental
Residue Curve Map (RCM)

phase split,

and condensate entrainer has largcl~ systems.

collects in decanter

as entrainer are reported"?

rich phase and entrainer for sending heterogeneous depends of entrainer

RCM'] is 3 geometrical tool to find feasible separation. column sequencing and optimum parameters for distillation operations. RCM are ternary diagrams remaining over a period curves. diagram displaying traces of liquid compositions result of vaporization traces are known technique". in a single batch still of time. These According is divided

to column.

Application

process of complex of suitable acid-water entrainer (AW)

a" a

of azeotropic batch distillation

liquid

for the system. was studied with

as residue saddles

to RCM into nodes regions. A a region.

any ternary

system

(stable and unstable). stable node is highest All residue curves

and distillation

certain entrainer

on lab scale a) decrease

in batch mode of operation in loss of acetic and b) reduced acid from time with hi,!,'h or banh
I

boiling vertex in a distillation node is generally region. where vertex.

in a distillation

region point towards lowest boiling curves all residue

layer of distillate: equilibrium assembly. ernraincr for a particular

reaction

stable node. An unstable vertex in any distillation will originate intermediate curves coming

controlled

reaction

configuration

from an unstable point in a distillation or g0ing node

10

A saddle point. an curve runs point.

two

Parameters inventory.

(role of reflux.mode and feed position [or

region. has neither residue it. Residue node via a saddle by joining

through stable

Author for correspondence Tel: 91 -020-30273670: Fax: Y 1-020-254427-70 Evrnail: principal_miICtlc@.milpune.com

from unstable Distillation azeotrope

boundary present

is a hazy line joining a stable node to in system

()f

formed

872
-----Table 1-

.I SCl lND RES

\'01. 611 OCTOBER

:n09

--~----.-

LL[ daia Ior AWT system" (experime rual ne lines In rnoleor 31 <lwe) Left phase Righi phase
-.-

SN("I

-------Acetic acid J.369 3.46:LS6' 7687 8.816 12.72:: 16.675 21091 24.126

Water

Arctic

acid

Water

..
5 I> 7 8

95.371 90.923 88.869 R5.R59 R2.310 79.24:'72.854 62.796 51U20

".~74 8.959 10.982 I~ 959 17.468 ::041>6 26.519 35.572 39517

0.507 0.753 0997 1.232 1.469 1.687 :.129 2.775 4.066

WATER

TOlUEf'iE(l

JOOr)

l\1oJe

0/.

azeoiropes in the system. It divides ternary plot into distillation regions. System was studied properly by vapor liquid equilibrium data for AW using toluene and benzene as entrainer. Tie line was compared for A\V with toluene. benzene and ethyl acetate. Results and Discussion
J. Acetic Acid -Water -Toluene (AWT) System

\V:t1tr

Fig. 1-1":lIure of residue curve !\'I acetic acid-water-toluene

~yqt"ln

Azeou ope Liquid Compos

it

ion

Vapor Cornposit ioo

". Disfilbtion bounchry

Liquid-liquid equilibrium (LLE) data (Table I) for AWT was referred from DECHEMAI4. In AWT. acetic acid is highest boiling vertex (BP I Igoe) and becomes stable node (Fig. I). There is presence of minimum boiling azeotropes between water and toluene at 84.4C (Azeo I) and acetic acid and toluene at I04.SoC (Azeo 2). Due to presence of azeotropes. entire ternary diagram is divided into three distillation regions (A, B and C). One of the distillation boundaries is formed between acetic acid and Azeo I and other between Azeo I and Azeo 2 (Table 2). In Region A, acetic acid is stable node, and water-saddle point and Azeo I is unstable node. In Region B. acetic acid is stable node. and Azeo 2-saddle point and Azeo I is unstable node. In Region C. toluene is stable node, and Azeo 2-saddle point and Azeo I is unstable node. Under vapor-liquid equilibrium (VLE) data, there is no much difference in region A between liquid and vapor composition. suggesting that for feed in region A, time required will be more (Fig. 2). In region C, stable node is toluene. so nature of distillate will be richer in toluene. which is undesired (Fig. I). Distillation in region 13was found to be more superior to be operated. There were significam jumps between liquid and vapor cornposuior for points in region B. indicating that with minimum time and stages one can get desired output.Intensity of jump

WATER

(100c) Auo

50'i'. J(!,14,4 c)
C

TO I. \![J"E( "0')

:::
1\101(' 'X, \\'~tt'r

Fig. 2- Triangular diagram she-w 109 selected VLE along with bimodal curve
ACET1C <\Cll) i,1U;:<'<l

--E- ----1\10h

":It<<'1

Fl~ ~- Fl~3~lhlerea-on 10I'p"" .:It,'\,. lumn (uccuc o toluene .\

,ll'lll}

~H'-

!J- \\ .ucr-

GADEKAR

('I

al: ENTRAINER

IOR I3ATel1 DlSTI LLATION

OF ACETIC

.ACID - WATER SYSTEM

8/3

Table 2Point number

Expcrirnenral

VLE darn for A\\ -I ternary

cornposuion

,~qrm
Vapor composuu-n

Liquid Water

Mole"c Accuc
3C

MQle'!c id
Water

Ar eric acid :;5.~~

I~)

R('XlOlI C

I 2
-l

J(I

I5

~o
2'1 9.11 2 157 5.3 7.14 0214 5.91 I 5.5<) 24.5 11.39 2-1.05 -10.,0 -I2.RO -11.27 }-I5 63.02 46.6 62:.4

.'

5
(-,

7 8 Region B 9 10 II
Rr!iiol1ll

101 100 10~.: 102 103 104 ID5 98 90.S

3535 ~5.97 :::; 40 39.2 9 41.5 :<2.55 J:l.3 1:\.67 53.-17 54.7 I 50.23 n.20 48.42 47.628 52.45 6::'.29 36.77 50.70 '7.36
--

7RS
:?)) '1-l

h:::

88
9.75 5911
I 7

34.2 :s -17 30.:?7 1:'.07 3050 28.848 17.36 lU

6904

2.3
55.8:6S 51.5 64.27 62 62.19 53.28 76.S 83.51 7::>.19

ns
10:'.5 101.5 10::> 92 94 100 101 IOU

30.2::'
-13 -'4.31 36.9 1) 7'2 :'409 22.35 15.90 :>7.39
- -----

12 1-' 14 15 16 17 18 19

-_.------

for some points is such that it shows acetic acid In aqueous phase. distillate be most distillate magnificent much to nature would composition favorable collected jumps.

only O-IOLiiJ io_~ of jumps with since some without ng B

I

Table 3-

Experimentat rexperirncntal Left phase

LLE data for :\v.:B system tie line in mok'H-! Righr

\\'3ICT

Points 9 and J 0 (Fig. :1) shows significant region indicating for column region efficient

SNo. Water 95.000 76.400 57.270 41.500 30.500

phase Acetic acid 2.943 10.780 23.482 30.000 40.000

below R9( tic line. Region B would operation has shown separation in this

Acetic acid 4.500 22.800 39.353 47.500 49.000

1.025 ~.933 6192 10.000 16 ()(){)

2
3
<1

loss of acetic

acid in aqueous in shaded

solution.

Accordi

of VLE data

in this region loss in acetic

and conceptual acid (0-2%) and

methodology,

feed position

portion of region

lead to negligible

may lead to less time in product

2. Acetic Acid -Water -Benzcne

separation.

stable node, Azeo 2- saddle point and Azeo J is unstable node. In Region C. benzene is stable node. Azeo 2- saddle point and Azeo I is unstable boundaries and other residue of is present distillation 4. In A WB a between acid node. One of the distillation acetic acid and Azeo I is between Azeo I and Nature of between boundary

(A'VB) System

LLE data for AWB system is given in Table 3. VLE

data stable benzene and azeotropcs. distillation boundaries for some points are given is presence at 70.5cC r Azco ternary in Table system, acetic acid is highest node. There and water entire regillns benzene boiling (Azeo ~). vertex and forms I) and acetic to presence of the distillation acid and Azco - saddle point B. acetic acid and is I is divided

Azeo 2. It is quite similar curves in region increasing It is similar

to AWT system, A is showing

of azeotrope Due

still path to be B. Entire

and become richer in acetic acid (stable node). nature of residue curves in region are approaching stable node acetic acid. C. space available is very small as acetic acid and benzene Distillate composit (9S'7c) is pure node. for feed points in ion, Presence 2) makes (Azeo

at 80cC

diagram

into three

(A, Band Azeo

O. One

residue curves In Region azeotrope this region of azeotrope near to benzene

is formed

bctw een acetic

I and Azco node. water ln Region

between

and other between Azeo I is unstable

2 (Fig. L In Region

A. acetic acid is stable

may exhibit azeotropic

node.

in acetic acid and benzene

.I SClI~D

RES

VOL f>R OCTOBER

2(lO')

A(L11C"

ACln

(l ,g<'c)

AC ETIC AODOJSCc)

Ii
,,101.% ACf',lc ~ /,

I,
.
/

1i
.

Acid

//
.

;/;

/~O"/o ,/"-

/
.I

/',,-+
I"
i

/j

>.----so-/.AZ) J(iOS'c)
BENZE..l"[.(SO.)C:c)

!LL __ ~

I /
~'" TR
(J

I c.=====:::::=====::::::::=;;~~~~=~'L..,2(8o-c)

OOOc)

~--ri~ ."- RCM and Ica-rble reason

10

operate column (aceuc acid,~,""em)

W;!ICr-OCJlICJ1C'

composition
Table 4: Experimental Point number Temp. VLE data for /\\\'B ~\'tl'm Vapor composition Mole'!c Acetic acid

in region B. whereas when feed composition in Region A. there is very small difference (point 7), indicating to bring desired are required

are falling between separation.

-c

Liquid composition Mole% Water Acetic acid 11.760 33 ""{lO 42.780 -16.362 -19.330 :'-1.400 2S.R20 6S.500

vapor and liquid composition Nature of residue

that large number of stages

---------Wain

curves for this system and

'.?

.,

79.50 ,9.50
79.R()

~ :;
6 7

7'1 SO
XO.OO R200 97.00 101.00

3850 6.370 13.3OC 14.54:; 1.397 3.450 69.120 26.080

0.970 6.9 Jlt -1.91()

') :;,In
II ~9S < 150 6~.870 82800

11.990 32.590 17.520 19.740 27.6<10 1:'>.320 29.380 16.360

shaded portion. which may give best separation. are shown in Fig. S. For feed lying in Region B and according 10 feed tendency. 0 wide gap is shown between distillate and bottom composition. It may be quite possible when feed is in shaded region, distillate composition number of stages in the column. AWT as an ernrainer is same to results AW B as an entrainer. In both systems, that will

ex hi hit only I 20/r loss of acetic acid at gain of minimum showing with

Table 5-

LLE data for acetic ac id- water-erhyl acetate (experimental tie lines in moleo/r at 30re) Left phase

system"

there is sure loss

of acetic acid in aqueous phase. This loss of component B (acetic acid) in Evlean phase and falling liquid level in sti II may hamper amount
acid

S No. Water I 2 3 4 18.547 22391 26.777 31.5) 3 34A57

Ri!1ht phase Water 97.329 96.236 94.975 93.791 92.804 Acetic

of heat transferred of tie line work, causes selection

and thereby a loss of is of entrainer composition

Acetic acid 3.091 5.892 8.368 10.504 12.332

vapor based given

flow rate.

Nature

0.899 1.762 2.666 3.-190 4.294

component

B. In current

on nature of tie line and decanter preference. has reverse water might (Table acetic nature

,--...,
!

If an entrainer it is more towards node, separation in of entrainer (AWE)" like

of tie line such as from entrainer Such is the case acetate there is only

node and away be quite simpler. acid

separation

tedious.

Ultimate

limit of residue

curves

-water-ethyl

this region is entrainer near to each as an entrainer. jumps. Distillate acetic acid showing higher other.

via an azeotrope. which is time

For feed in region very and not benzene

system

5). In this system,

C points I and 2 show vapor suitable for distillation

and still composition consuming Even by having

one minimum boiling azeotrope present between water and ethyl acetate at 70.4cC. Ternary plot is therefore divided into tw o distillation chances regions. regions. As number separations. approaches of

operation.

fced portion collected jumps.

in region B i~ showi ng good was having vcr y less loss of fl. ~ and h a v i ng -I are feed Pointwere

azcoiropcs increases.
thcr cby reducing n.uurc both distillation of residue curve

complexities

in column increases. From stable it is found that in

of feasible for thc system. residue curve

in aqueous

phase. which

C.'\DEKAR

tf

"I. ENTRAINER

FOR 13/\TCH D1S11LLI\TION

OF ACETJC .-\CJD -WATER

SYSTEM

875

ACr.TI(

AUD

(l18"c)

tendency important

to form azeotrope with acetic acid is also factor; entraincr that does not form azeotrope In other words, less is the amount is the tendency to

r"\101f'

Cj'e

-\UOllf

Ar-id
/.

/~ '

t"

.
\

Dhtilbllon bound2r)

\\
\~.
\

with acetic acid should be preferred. less the number of distillation regions of complexities achieve in column and more pure product.

\.
'\,~-;" .

\ .\

.. .., /
\ Ii,> I

-;\.
;

1 \

,.'.~
:'\1olf'
"/0

Ref'er e nces
F..lh~1 AH'f21f

\,

.
/_---

\
ACETATEI77"C)

ETHYL
f\1ol~

'Y".

\V2tt'r

FI~

(>

Nature 01 tIC line tor acetic acid-water-cthvl

acetate ~y"cm

node acetic system.

acid only. At heterogeneous approx . only

region

in AWE there

it covers

20%. Therefore.

are fewer chances of complexities in column. If one considers same feed positions of feasible region B for toluene and benzene as an entrainer in same position for ethyl acetate as an erurainer and compare with nature of tic line. one would find that in most of the cases there will he 0ge loss of acetic acid in aqueous phase. This i~ purely due to opposite towards (Fig. 6). Conclusions AW processes. prerequisite, eliminated. distillation system has mystery in much VLE study and distillation and benzene. industrial of the system products is Region B was Proper experimental like for toluene water nature of tie line. which from ethyl is more node node and away acetate

to study nature of the bottom found to be favorable,

yet acid loss was not completely

Working with these entrainers, three regions, which add up to complexities in of tie line is important free disposal of water. pure

column, were found. Nature parameter to consider acid Entrainer good system like ethyl acetate water node is considered separation phase. aqueous

having tie line towards loss of acetic with acetic regions. acid

a good option and may result in acid in water Entrainer

and negligible

This

entrainer

leads to only two distillation

Chrisune B. Doherty M I & Malone M F. Feasibrlity and separation sequencing In mulncornponent batch distillation. J Chern Engg Sri. 46(1991) 13111326 . 2 Hrlrnen EK. Sepurnuon of fI:t'(JII()P" mixtures: Tools for analavsis and srudirs (In butch distrllution operations, Ph D Thesis. I orwe g ian Univ ersilY of Science and Technology. Norway. 2000. :; Rodriguez-Donis L Pardillo-Fonrdcvila E. Gerbaud v & Joulia x. Synthesis. e xpcrirncnts and simulation of bererogcncous batch distillation processes. Compu Chem Engg, 25 (2001) 799806. " Rodriguez-Donis I. Gerbaud v &. Joulia X. Feasibility of hererogeneous batch disullanon processes. AIChE J. 48 (2002) I 168 1178. 5 Rodriguez-Donis I. Esquijaro-.a J A. Gerbaud V & Joulia X. Heterogeneous batch-extractive disti llation of minimum boiling azeorropic mixtures. AIChE J. 49 (2003) 30743083. 6 Modla G. Lang P. Kotai B & Molnar K. Batch betcroazeorropic rectification of a Low mixture under continuous entrainer feeding. AIChE J. 49 (2003) 25:;32552 7 Skouras S. Sk ope smd & Ki\ 3 V. Analysis and control of hereroazeouopic hatch dl~t"lati"n. J AIChE. 51 (2005) 1144 1157. 8 Gadekar S V. 'JiJ.. R V & Bapat J D. BalCh distillation parameters for heterogeneous azeouopic s~ sterns. J Chern Engg World. 42 (2007) 44-50. 9 Skouras S. Kiva V & Skogesrad S. Feasible Separations and entraincr selection rules for hereroazeorropic batch distillation. J Chem Eng~ Sri. 60 (2005) 28952909. 10 Rodriguez Donnis I. Gerbaurd V & Joulia X. Entrainer selection rules for the separation of nzeotropic and close boiling temperature mixtures by homogeneous batch distillation process. J Ind Eng Chern Res. 40 (2001) 27292741. I I Lung Chien J, Kai -Luen Z. Huan- Yi C & Jung Hong L, Design and control of acetic acid dehydration system via heterogeneous azeotropic distillation, J Chern Engg Sci. S9 (2004) 4547-4567. 12 Doheny M.F & Malone ME Conceptual Design of Distill orion Systems (McGraw-Hill. 1'e\ York) 2001. 13 Gert-Jan A E Fien & Liu Y A. Heuristic synthesis and shortcut Design of separation processes using Residue Curve Maps. J Ind Eng Chem Res. 33 I 199J) :?5052522. 14 Nar s irnb a Rao P & Mur t h v D. Chemistry data series. DECHEMA.S (19 0) 28,290 15 Sohoni V R & Warhadpande L' R. System ethyl acetate- acetic acid -w3tCL J lnd EII,~Clu m, ~ I I,}S~) 1.::>8. I

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