IICPT
Engineering
andPetroleum
of Chemical
lraqiJournal
13-18
2007)
(September
Vol.8No.3
ISSN:1997-4884
lr^qi Journal of Chcmicsl
end Petroleunr Engineering
Univ.6iq of Brthdrd
Collcgc of Enginering
of HydrogenPeroxideby BatchDistillationColumn
Concentration
I' Ghulam
AbbasH. sulaymon,Abdul-RezzakH.Al-Karaghoulinand sattar
- rJniversity of Baghdad - Iraq
Environmental Engineering Department college of Engineering
Abstract
ffict of
of hydrogenperoxideby va|uurydistillation'The
to studythe concentration
was conducted
An investigation
used
column
of
the
refluxratio, ti^i of dittitiotion,andpackingheight
variables(suchas vacuumpressure-,
the process
of
stage
the
third
During
hydrogenperoxidewere invesiigated.
on the concentration"of
in the distillation process)
wasobtained'
(95wt.%)concentration
clistillation
workfor the mentionedvariables'It
desrgnis usedto designthe experimenral
rotatable
Box-Wilsoncentralcomposite
pressure,decreasingreflux
vacuum
wit.h:Tncreasing
wasfound that the concentrationof hydrogen'peroxide,increaies
ratio, increasingthetime of distitlaiionqnd increasingthepackingheight'
of hydrogenperoxide)'with
(concentration
Thesecondorderpolynomialregressionanalysis$the obiectii, ,ripontt
equations:
programgavethefollowing
to thefour variible, usingitatistical
respect
H2
R2- 0'0035
- 0.27P - 81.45
t + 0.69H + 55.67
R! 16.36
Yt = 54.87
/
+
n2- S',ss
105'25
+
P2
0'0018
i
H
t
+
O.Zt
R tg.B'
Yz= 1 04.04 0.44P 140.62
*
/
2'75
R2
26'78
P2
H
0'0047
o.ogl
+
t
y: = 83 79 0.18P 1g.04
R I 3.14
Keywords:hydrogenperoxide,batchdistillation'
is classifiedas "Corrosivematerial".Actuallyhydrogen
weakacidt21.
peroxideis extremely
chemical
products
of hydrogenperoxide(10 to 70
Commercial
Hydrogenperoxideis a major industrjal
of
impuritiessuchas metallic
scale
in
contain
usually
wto/oH2O),
material-which is rapidly increasing
impurities(NO3,POa,
inorganic
and
Rtuminum)
andusest'r.
1tron,
manufacturing
increased
have
use
and
SOo;trl.
Its scale 6f manufacture
are usedto
A numberof the purificationtechniques
markedlysinceabout 1925when electrolyticprocesses
as
to theUnitedStatesandindustrialbleach remove metallic and inorganic impurities such
wereintroduced
and
distillation, crystallization,adsorption,filtration
applications
'i{ydrog"n weredeveloPedt2l.
of
peroxidecan be preparedelectrochernically reverseosmosis.Dependingon the degreeof puriry
of
these
stages
by t'heoiiOuiion of sulfuric acid or the partial reduction hydrogenperoxideaddition of more
arerequiredt'1.
methods
oi Oz. And by catalytic process' such as the
processl".
anthraquinone
I{ydiogen peroxide solutions are strong oxidizing
ExperimentalWork
agents.[n somecases,hydrogenperoxidealsoactsarea
Apparatus
rJducingagentbut only toward thosematerialsthat are
solutions
acid
in
e'g,
oxidizingagents,
themsel"veJstrong
Hydrogen peroxide was concentratedby using a vacuulrl
to
a
hydrogenperoxidereducespotassiumpermanganate
distiilatio; uppu*no. The vacuum distillation unit consistsof
(52
wt'%)
above
peroxide
Hydrogen
*ungin.t" sulfate.
andvacuumunit Fig. (1)'
distillationapparatus
lntroduction
2007)
IJCPEVol.8No.3(SePtember
Concentration of hydrogenperoxide b. batch vacuum distillation
,,,&;{'rr
Fig. I Vacuumdistillationunit
1- Water Bath: The water is heated by means of
electronical immersion coil placed inside the bath'
Electricalpower to the immersioncoil is regulatedand
providedby adjustmentsof the voltage regulator.The
water bath is capableof holding two still pot flasks of
(250 ml) volume each.The still pot has a 2'necksround
boffom Pyrex flask. One neck is used for thermometer
while the otheroneusedfor the connectionwith the other
flask which has three necks. The thermometeris
immersedto about(2 cm) abovethe flaskbottom'
2- The packed column: The experimentsin the present
work were carriedout using a (2 cm) I'D glasscolumn
filled with 5 mm glass Rashingrings. The column is
desigred for a batch rectification process.It has two
branihesfor placing the thermometerfor measuringthe
temperatur€. One of these branches contains a
terrromaer which measuresthe temperature of the
eoteringyaps to the baseof the column and the other is
us€dto m€asrre the temperatureof leaving vapor from
thecolumn
! Divllcn Reffux divider is placedbetweenthe column
md condmtr. Divider is usedto give an adjustableratio
b€twe€nfu t*Eofr water distillate and the reflux' The
heightof rtc dividcr is (20 cm) with an outer diameterof
(3.i cm). Tb€ diYidrr has two branches for placing
thermometer.Onc of thesebranchesis used to measure
the temperalrre of fre vryor while fr€ other branch is
usedto measurethe temperanreof the liquid condensate'
The distillate liquid is collectedin the round flask which
is connectedwith tube to transfertbe liquid condensarcto
thecontrollingdevicewhichadjustsreflux ratio.
4- Condensei: The dividerwasconnectedto the helicaltube condenserwhich is (30 cm) height and (3'5 cm)
x4
outer diameter. The condenserhas two nozzles for
cooling water flow. The top of the condenser'\ryas
to the vacuumline,
connected
5- Receiver: The receiverwith volumeof (150 ml) is
connectedto the vacuum line through two solenoid
valuesto confrolthe flow ofthe condensate.
The bottom of receiverwtrs connectedto a round flask
with volumeof 250 ml.
6- VacuumUnit :
The vacuumlines from the condenserand the receiver
werejoined by meansof -T- shapevalve, The resulting
connectionis called main vacuum line. Two traps are
connectedto the main vacuum line' These traps are
cooledby liquid nitrogento protectthe vacuumpump
from entrainingvapor and liquid. One of the two outlet
linesfrom the trapswasconnectedto one-wayvalve,and
the other was connected to the vacuum pressure
controller.
The vacuumpressurecontrollerwas used to adjustdtc
pressuredrop in the distillationsystemby comparingthc
vacuumpressureset valuesand vacuumpressurevalues
in thetrapindicatedby controllersensor.
The controllersendsits signal to the one-wayvalve to
openor plosethe vacuumline dependingon the vacuum
pressurein the traP.
The one-wayvalve is connectedto rotary vacuumpunp
which producea vacuumpressurein the system'All para
of theequipmentaremadeof glass.
Procedure
Experimental
The vacuumdistillation experimentswere carriedql
as shownin Fig
by usinga vacuumdistillationapparatus
(l).
andjoins L
all connections
Beforeeachexperimental
grease
in orderto
by
silicon
lubricated
were
the apparatus
for eacl
feed
pressure'
The
vacuum
obtain the desired
peroxi&
hydrogen
ml
of
was
100
experiment
distillation
(25, 50, 75 wt'%
solutionwith definedconcentration
HzOd. This quantitywas chargedinto the still pot then
evaporation takes place, followed by distillation
expirimentwhereproceedsfor a certaintime anddefined
vacuumduringthe oPeration.
Samplesfrom the desired product, residue and the
condensatewater are taken for analysis of hydrogen
peroxideconcentration.
After each experiment all parts of the vacuum
distillation apparatus are washed with demineralizsA
water in order to remove any possible contaminants
still pot'
in the column,condenser,
accumulated
operation of
an
was
procedure
washing
The
demineralized
(250
of
ml)
using
aisiittaiion
atnospheric
waterto washthe contaminantsand accumulatethem at
the bottomof the still pot wheretheycanbe removed'
arethe sameas for threestagesto get
Theseprocedures
hydrogenperoxide(90'95 wt'o/o)'
a highly concentrated
2007)
IJCPEVol.8No.3(September
hydrogenperoxideobtained
The higherconcentration
pot
numbertwo' While the
was collectedin the still
still pot number one
the
in
of residue
concentration
to removeimpurities'
off
drawn
be
whichmust
increased
in the receiverand
collected
is
The water distillate
flask.
collection
After the distillationprocessis preformedthe vacuum
system is switched off and the required hydrogen
ffom the distillationsystemand
peroxideis separated
storedin refrigerator.
Resultsand Discussion
of Results
Analysis
by the
The response of experiments represented
to. the
fitted
is
which
peroxide
concentrationof hydrogen
conclltlons
operating
the
results, was used to determine
for each
that give the concentrationofhydrogen peroxide
distillation'
stageof the vacuum
Similarly the relation between h; droger 3eita\"1:
uas ploned:o::ire:
c o n c e n t r a t i oann d v a c u u mp r e s s u r e
(3) The n:rnes:
Figure
in
shown
as
distillation
times of
\\'ereoetsln3;
valuesof hydrogenperoxideconcentratlon
e:
at longer times of distillation, but it * as o.fs:n
(1
h:t:'r:
5
experiientally that the best time was about
lh:
the experimentconditionsused,It was obsen'edthat
a:
produced
stabiliiy of hydrogen peroxide solution
because
high
(2.5
was
not
hr)
longertime of distillation
the organic impurities evaporatedalong with h1'droeen
in
p.ro*ii. product and the concentrationof impurities
level'
hazardous
ihe residui possiblyreaches
to
Thereforethe optimum vacuum pressureis essential
highest
with
product
of
concentration
desired
achievethe
loss'
purity and consequentlymore stablewith minimum
It I -(t.fi
Models
Mathematical
:.: r ri
IlI=0.('
I
l{"1=il.5
l
l{{=0..1
a l{i'(1..i
form
A secondorder polynomial which has the general
the
of
range
the
in
was
employed
fbr four variables,
following
the
by
represented
as
variable,
indenendent
equation:
y : B o + B 1 X 1 + B 2 X 2 + B 3 X 3 + B r X r + B 5 X 1 X 2+
+
+
BeXrX: + B7X1Xa+ B3X2X3+ BeX2Xa B 1 6 X 3 X a
(1)
.,
!
ii 1
l
1
,.1
1 . I. 5 ( h f l
l l = 0 1 (Jc r t l )
,:l
l
jr*---'1'-.''r
I ll
X:r il. ,X,+ ii ,X:
llr
i(l
l(l
:Lr
jlrll
!1t
;{}
blr
lll
\ r c t t t t t t tl ' t l s r l t r t l t t t t t l l l l )
Effectof VacuumPressure:
vs' vacuum
Fig. (2) : Hydrogenperoxideconcentration
of
on the concentration
The effectof vacuumpressure
pressureat variousreflux ratios
the
hydrogenperoxidewas studiedin orderto determine
distillationprocessis bestperformed'
;i.;t;;d*hich
'
j
eil i
that for all reflux ratiosstudiedthe
(2)
show
\
tl=l.irlrrr
Figur.
'!
as the
increases
peroxide
s
:
r 1-: ihr)
hydrogen
of
conJentration
-\
at
(hrl
rl-,1.5
vu"uut pressureincreases'Figure (2) shows that
'r,
.l=lllrr)
r
appearsro
peroxide
ofhydrogen
.\
R=0.3th; concentration
ri ,.i,lrr,
sincethe
=- _-__o
i*u. ,fr. highestvalue but it is not desired'
..--.-r
is
distilled
water
with
':
---;---"''--* - arnountof hydrogenperoxidelost
i,il
"-:If-r--=--..=--..-..-- -:l
first stage
&.=-*u*l*ut. ttretJtort'ttte best reflux ratio for
d i s t i-Ji"t"
llationwasfoundtobe(0.5-0.6)thisrangeofreflux
="
the desired concentrationof hydrogen
r.ii"
Iltr.i
'
l l = ( r ((l f r l r)
peroxideandminimumloss'
water
the
in
peroxide
hydrogen
of
The concentratton
I|
lil
.jistilledisincreasedwhenthevacuumpressurelncreaseo
the best
Yrctltttlt l'rtrsttrt (ttttttllgI
unJ the reflux ratio decreased'Therefore
conditionfbrconcentrationofhydrogenperoxidewas
vs' vacuum
concentration
peroxide
Fig.(3) : Hydrogen
range(80-60mmHg)
foundto be in the vacuumpressure
at varloustlmes
stageand
Pressure
fo, ir.rt stage,the (60-40mmHg) for second
(30-20mmHg)for thirdstage'
Effectof RefluxRatio
of
the concentration
The vacuumpressureini'luences
C:
mainly the
The effect of reflux ratio on the concentration
hyarog"n p.ro*id, in different ways'
c:
tille
to avoid the
nyarog.n peroxideat a given (vacuum.pressure'
operationat low pressureis normallyused
(6)'
(76 wt'o/oHzOz Oistillition),is shownin Figures(5) and
of explosivevaporcomposition
i'J.rnution
impurities'
organic
the
andabove)andieavingUeiina
.li ---
\!l
-i
?
:
'---l]=-.--
ii
3iil
a
-
l
tl
r,t
ii
_ i { l1 -
---
T - --'
2007)
IJCPEVol.BNo.3(SePtember
tIi
-
_
Concentrati on of hydrogenperoxide by batch v Qcuumdistil!!\9!_
Examiningthese Figures it can be seen that the
hydrogen peroxide concentration increases with
decreasing
the reflux ratio. For exampleat R=0.3 the
of hydrogenperoxidewasthe highest,but
concentration
it is not desiredfor first and secondstagesof vacuum
distillation, becausethe concentrationof hydrogen
peroxidelostin thedistillatewateris maximum.
Therefore
theoptimumrefluxratioin first stageis (0.50.6) and in secondstage(0.4-0.5).But in the third stage
optimum reflux ratio is (0.4-0.3) for limited the
concentrationof hydrogenperoxide in distillate water
usingpackingheightof (80 cm).Refeningto Figure(4),
which clearly illustratesthat the lossesof hydrogen
peroxidein the waterdistillateincreasewhenthe reflux
ratiodecrease.
Thebestrefluxratiois theratiowhichgivesthedesired
concentrationof hydrogen peroxide product and
minimumloss.
';'-- s r:l
li
-li
i
l
I'i
.:
I
l
('{l .l
I
l
1
l
:01
ti
.lt I
li
J
l
j
1
.---.-a-.---,-*-_-
l l = 6 1 () r r I )
_.
--. a
1__
1r.:
lt.l
ili
0:
{rfi
rrli
l{rllur llrtirr
vs.reflux
Fig.(6) : Hydrogenperoxideconcentration
ratioat varioustimes
' ri
'l j
. | ,j
1 . . I - I i r ( l( r l t r llrl '
l)
r p l = l i l )t r r r r l l l _ t
I l1t
. 4 . J r . l - t , {l)r l r r r
p { = 1 ( il r n r n l l l )
.'\r .
1 r j = l l l( r r t n tllg ) . - , a - '
t
..- ,-a-"'
..i-'
''
l
-
..4
,a"',,.a''
-t'
..---,1-'.-.-.--''
,--J'
'd....
li -{1.5
l l = ( ) l l{ U r ) )
l s
lr.0
_ _-_
-=-
j
l.::
0.r5
0.15
0..15
R r f l u rl l ; r t i o
in water
Fig.(a) Hydrogenperoxideconcentration
ratio
distillatevs.reflux
1 . . I ' . . l { l l ll t t t t t t l l :
t , l ' - S ( l{ n r r n l l ! t
r ' . . l ' = ( ' 1 i1n 1 ! r l l : l l
1 . . l ' l t l ( n r n lrl i i
l. l' .,:ll lrttrtrll'll
a
I
\
\
t.
'
)
'-l-
r.'i.51hr)
I | . , 0 (llc n r l
1t.i
1 r l.
lt I
\
llrlltrr I{:rtirt
Fig. (5) : Hydrogen peroxide concentration vs' reflux
ratio at various vacuum Pressures
16
vs.timeat
Fig.(7) : Hydrogenperoxideconcentration
variousvacuumPressures
Effectof Timeof Distillation
The best time of distillationis an importantfactor
of hydrogenperoxide,which
affectingthe concentration
of
must be known to avoid the rise of concentration
hazardous
product
to
peroxide
impuritiesin thehydrogen
level.
of distillationis batchwise,therefore
Sincetheprocess
so thal
therateof evaporation
to determine
it is essential
the time requiredshouldbe just sufficientto evaporate
about80-90%ofthe originalfeed'
ExaminingFigures(7) and (8) it can be seenthat the
concentrationof hydrogen peroxide increaseswith
thetimeof distillation.
increasing
It is clear from those Figuresthat when time oi
ofhydrogen
distillationis equal(2.5hr) theconcentration
peroxideis highest.But the product was not stable'
alongwith the productand
b"causeimpuritiesevaporated
theamountof residuewasvery little (3-5 ml) out of (10(t
ml) is originallyfed. But when time was (l'5 hr) the
2007)
IJCPEVol.BNo.3(SePtember
amountof residue(10-15ml) andtheproductwasstable
thereforethe best distillation time which leads to a
desired concentrationof hydrogen peroxideis greatly
dependentorirthe specificconditionsof the experiment
(i.e., amount of hydrogenperoxide,vacuum pressure'
temperature).
\ ttr=o,s
\tu=o.o
\ n:=n.r
\ Hr=o.t
\
tts=tt.l
P=li(l rDnrll{.1
l l = ( r l l( e n t )
0.:
1.0
lt.6
l.l{
l.l
'I'inrclhr).
areaof distillationcolurnnpacking,,then it follows tb*
high surface areas result in high heat and materidtansfer, Maximum efficiencyis obtainedby using lutg
columnsof highsurfacearea)161.
Thesefigures show also that for first and secondstage
the best packingheight is (60 cm) becausethis leight
gives the desiredconcentrationof product and minimum
lossof hydrogenperoxidein waterdistillate.In the third
stagehowever,the packing height used was (80 cm)'
Sincethe feed to this stageis relativelyhigh (75 wt'7o)
lossesofhydrogenperoxidein the
andto avoidbxcessive
water distillate and to achievethe desiredconcentration
of product(> 90 wt.o/o).
When packing height of (1 m) was used a high
concentrationproduct of hydrogen peroxide was also
obtained,but a problemof'flooding was observed'(this
problem is not desired and.-.can be prevented by
flectricallyheatingthe column)t7].
\lt t*
l.l)
vs,time at
Fig. (S) : Hydrogenperoxideconcentration
variousreflux ratios
:u
sr.
IrlJ
t
':
:i t u
irs
9.:
tt.:
\
::.5
:
O :
J
i
-*- '-----
'\
\
\
\
\
p l = l l X ){ r l r n l l g )
p 1 = 8 {l ln r n r l l g l
p . 1 = 6l0m n r l l g )
p J = { 0( r n n r l l g )
p 5 = 2 0( n r r l l l g )
ffi
JIJ
.tl
-:.:
jil
0
.:1.5
:tr
\.
t
r
1
, i.l
v
t.r'1
.lr|
{ili
lt0
ll}0
l)atking I'ltighl ( cnt )
Fig. (10) : Hydrogenperoxideconcentationvs. packing
heightat variousvacuumpressures
\-,-"----.-*-*,t
. " i
il \1
.0 i i--'.-'''_---*---
l0
.r0
.i(l
:0
llii
l ' ; r r l i n gl l c i g h{t c n tt
t0
in water
Fig, (9) : Hydrogenperoxideconcentration
distillatevs. Packingheight
.n
l ' = { 1 0( n r n r H g )
t = 1 . 5( h r )
S-r
3ri
\
Effectof PackingHeigrht
. ii
The effect of packing height is clearly observedby
distillate'
water
in
peroxide
hydrogen
concentration
Examiningflg*t (9), it can be seenthat increasing
packing tre'igbt"will decreasethe concentrationof
peroxidein thewaterdistillate'
irydrogen
-Figires'(10)
and (ll) showthat increasing^ofpacking
l'rcl,irr* | l.ight (crl)
neig[t wiit increase the concentrationof hydrogen
perixide product (The efficiency of distillation column
Fig. (11) : Hydrogenperoxideconcenfiationvs' packing
material
*9
ht*
transfer
dependsupon its ability to
heightat variousreflux ratios
beiweenthe liquid and vapor sueams'Since,in the case
ofpackedcolumn,this transfertakesplaceon the surface
2007)
IJCPEVol.8No.3(September
Concentration ofhydrogen peroxide by batch vacuum distillation
Gonclusions
Nomenclature
The following conclusionscould be drawn from this
investigation:
l-The secondorderpolynomialregressionanalysisof the
objectivefunction i.e., the concentrationof hydrogen
peroxide and four variables (i.e., vacuum pressure,
reflux ratio, time of distillation,and packingheight),
for eachstagesof distillationwerefound.
2-lt is necessaryto concentratehydrogenperoxideby
using vacuum distillation in two or three stages
because:
a-Decreaseof the boiling point of hydrogenperoxide
leads to decreasethe rate of decompositionof
hydrogenperoxide.
b-Obtaining hydrogen peroxide with high purtty and
goodstability.
3-The concentrationof hydrogen peroxide increases
with:
aIncreasingthe vacuumpressure.
bDecreasing
the reflux ratio.
cIncreasingthetime of distillation.
dIncreasingthe packingheight.
4-The bestoperatingconditionsto concentrate
hydrogen
peroxideare:
aFirst stage:
iVacuumpressure(80-60mmHg).
ii.
Refluxratio(0.5-0.6).
iiiTimeof distillation(l.5 hr).
ivPackingheight(60 cm).
bSecondstage:
iVacuumpressure(60-40mmHg).
iiRefluxratio(0.4-0.5).
iii- Timeof distillation(1.5hr).
ivPackingheight (60 cm).
cThird stage:
iVacuumpressure(30-20mmHg).
iiRefluxratio (0.3-0.4).
iiiTimeof distillation(1.5hr).
ivPackingheight(680 cm).
H
PackingHeight.
m
P
VacuumPressure.
mmHg
R
RefluxRatio.
t
Time.
Y
Calculated Value of
(Concentration
of HzOz).
18
hr
the
Response
References
I'Green Wood N. N. EarnShowA., "Chemistryof the
Elements",John Wily.and Sons Inc., New York,
(1e98).
2-DavisS.N., KeefeH. J.,"Ind.Eng.Chem.",Vol.48,P.
745,(t956).
3-Hampel A. Clifford, "The Encyclopedia of
EIectr ochemistry", (1964).
4-Kajiwara,et al, U. S. Patent,5, 534, 238, July, 9,
(19e6).
5-Ledon,et al, U. S. Patent,6, 187, 189,February,13,
(2001),and U. S. Patent,6, 183, 638, February,6,
(2001).
6-SkidmarR., "QyF TeachingSystem",ComingLimited,
(1986).
7-Kerl 8., "Hand Book of Laboratory Distillation",
(1982).
ElsevierScientificPublishing
Company,
8-GiguereP. A., "Cand.J. Chem.",Vol. 32, P, 117,
(l 9s4).
2007)
IJCPEVol.8No.3(September