IICPT

lr^qi Journal of Chcmicsl

end Petroleunr Engineering
of Chemical
lraqiJournal
Vol.8No.3 2007)
(September
ISSN:1997-4884
Engineering
andPetroleum
13-18
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
to studythe concentration of hydrogenperoxideby va|uurydistillation'The ffict of
An investigation was conducted used
refluxratio, ti^i of dittitiotion,andpackingheight of the column
the process variables(suchas vacuumpressure-, stage of
hydrogenperoxidewere invesiigated. During the third
in the distillation process) on the concentration"of
clistillation(95wt.%)concentration wasobtained'
rotatabledesrgnis usedto designthe experimenral workfor the mentionedvariables'It
Box-Wilsoncentralcomposite
wit.h:Tncreasing vacuum pressure,decreasingreflux
wasfound that the concentrationof hydrogen'peroxide,increaies
ratio, increasingthetime of distitlaiionqnd increasingthepackingheight'
(concentrationof hydrogenperoxide)'with
Thesecondorderpolynomialregressionanalysis$the obiectii, ,ripontt
programgavethefollowing
to thefour variible, usingitatistical equations:
respect
Yt = 54.87 - 0.27P - 81.45 R! 16.36 t + 0.69H + 55.67 R2- 0'0035 H2
- - +
R tg.B' i O.Ztt H + 0'0018P2 + 105'25 n2- S',ss
/
Yz= 1 04.04 0.44P 140.62 * -
- -
y: = 83 79 0.18P 1g.04 +
R I 3.14 t - o.ogl H - 0'0047 P2 26'78 R2 2'75 /

Keywords:hydrogenperoxide,batchdistillation'

is classifiedas "Corrosivematerial".Actuallyhydrogen
lntroduction peroxideis extremely weakacidt21.
Hydrogenperoxideis a major industrjal chemical Commercial products of hydrogenperoxide(10 to 70
material-which is rapidly increasing in scale of wto/oH2O), usually containimpuritiessuchas metallic
manufacturing andusest'r. 1tron, Rtuminum) and inorganic impurities(NO3,POa,
Its scale 6f manufacture and use have increased SOo;trl.
markedlysinceabout 1925when electrolyticprocesses A numberof the purificationtechniques are usedto
as
wereintroduced to theUnitedStatesandindustrialbleach remove metallic and inorganic impurities such
distillation, crystallization,adsorption,filtration and
'i{ydrog"n weredeveloPedt2l.
applications
of
peroxidecan be preparedelectrochernically reverseosmosis.Dependingon the degreeof puriry
stages of these
by t'heoiiOuiion of sulfuric acid or the partial reduction hydrogenperoxideaddition of more
oi Oz. And by catalytic process' such as the methods arerequiredt'1.
anthraquinone processl".
I{ydiogen peroxide solutions are strong oxidizing ExperimentalWork
agents.[n somecases,hydrogenperoxidealsoactsarea
rJducingagentbut only toward thosematerialsthat are Apparatus
oxidizingagents, e'g, in acid solutions
themsel"veJstrong Hydrogen peroxide was concentratedby using a vacuulrl
hydrogenperoxidereducespotassiumpermanganate to a
distiilatio; uppu*no. The vacuum distillation unit consistsof
*ungin.t" sulfate. Hydrogen peroxide above (52 wt'%)
distillationapparatusandvacuumunit Fig. (1)'

2007)
IJCPEVol.8No.3(SePtember
Concentration of hydrogenperoxide b. batch vacuum distillation

outer diameter. The condenserhas two nozzles for

cooling water flow. The top of the condenser'\ryas
connected to the vacuumline,
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
,,,&;{'rr
controller.
The vacuumpressurecontrollerwas used to adjustdtc
pressuredrop in the distillationsystemby comparingthc
Fig. I Vacuumdistillationunit vacuumpressureset valuesand vacuumpressurevalues
in thetrapindicatedby controllersensor.
The controllersendsits signal to the one-wayvalve to
1- Water Bath: The water is heated by means of openor plosethe vacuumline dependingon the vacuum
electronical immersion coil placed inside the bath' pressurein the traP.
Electricalpower to the immersioncoil is regulatedand The one-wayvalve is connectedto rotary vacuumpunp
providedby adjustmentsof the voltage regulator.The which producea vacuumpressurein the system'All para
water bath is capableof holding two still pot flasks of of theequipmentaremadeof glass.
(250 ml) volume each.The still pot has a 2'necksround Procedure
Experimental
boffom Pyrex flask. One neck is used for thermometer
while the otheroneusedfor the connectionwith the other The vacuumdistillation experimentswere carriedql
flask which has three necks. The thermometeris by usinga vacuumdistillationapparatus as shownin Fig
immersedto about(2 cm) abovethe flaskbottom' (l).
2- The packed column: The experimentsin the present Beforeeachexperimental all connections andjoins L
work were carriedout using a (2 cm) I'D glasscolumn the apparatus were lubricated by silicon grease in orderto
filled with 5 mm glass Rashingrings. The column is obtain the desired vacuum pressure' The feed for eacl
desigred for a batch rectification process.It has two distillation experiment was 100 ml of hydrogen peroxi&
branihesfor placing the thermometerfor measuringthe solutionwith definedconcentration (25, 50, 75 wt'%
temperatur€. One of these branches contains a HzOd. This quantitywas chargedinto the still pot then
terrromaer which measuresthe temperature of the evaporation takes place, followed by distillation
eoteringyaps to the baseof the column and the other is expirimentwhereproceedsfor a certaintime anddefined
us€dto m€asrre the temperatureof leaving vapor from vacuumduringthe oPeration.
thecolumn Samplesfrom the desired product, residue and the
! Divllcn Reffux divider is placedbetweenthe column condensatewater are taken for analysis of hydrogen
md condmtr. Divider is usedto give an adjustableratio peroxideconcentration.
b€twe€nfu t*Eofr water distillate and the reflux' The After each experiment all parts of the vacuum
heightof rtc dividcr is (20 cm) with an outer diameterof distillation apparatus are washed with demineralizsA
(3.i cm). Tb€ diYidrr has two branches for placing water in order to remove any possible contaminants
thermometer.Onc of thesebranchesis used to measure accumulated in the column,condenser, still pot'
procedure was an operation of
the temperalrre of fre vryor while fr€ other branch is The washing
aisiittaiion using (250 ml) of demineralized
usedto measurethe temperanreof the liquid condensate' atnospheric
The distillate liquid is collectedin the round flask which waterto washthe contaminantsand accumulatethem at
is connectedwith tube to transfertbe liquid condensarcto the bottomof the still pot wheretheycanbe removed'
thecontrollingdevicewhichadjustsreflux ratio. Theseprocedures arethe sameas for threestagesto get
4- Condensei: The dividerwasconnectedto the helical- a highly concentrated hydrogenperoxide(90'95 wt'o/o)'
tube condenserwhich is (30 cm) height and (3'5 cm)

x4 IJCPEVol.8No.3(September
2007)
 hydrogenperoxideobtained Similarly the relation between h; droger 3eita\"1:
The higherconcentration uas ploned:o::ire:
pot numbertwo' While the 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
was collectedin the still in Figure (3) The n:rnes:
the still pot number one times of distillation as shown
concentration of residue in
valuesof hydrogenperoxideconcentratlon \\'ereoetsln3;
increased whichmust be drawn off to removeimpurities' e:
is collected in the receiverand at longer times of distillation, but it * as o.fs:n
The water distillate (1 5 h:t:'r:
experiientally that the best time was about
collection flask. lh:
the experimentconditionsused,It was obsen'edthat
After the distillationprocessis preformedthe vacuum produced a:
stabiliiy of hydrogen peroxide solution
system is switched off and the required hydrogen (2.5 hr) was not high because
ffom the distillationsystemand longertime of distillation
peroxideis separated
the organic impurities evaporatedalong with h1'droeen
storedin refrigerator. in
p.ro*ii. product and the concentrationof impurities
ihe residui possiblyreaches hazardous level'
Resultsand Discussion Thereforethe optimum vacuum pressureis essential
to
desired concentration of product with highest
of Results
Analysis achievethe
loss'
purity and consequentlymore stablewith minimum
by the
The response of experiments represented
peroxide which is fitted to. the
concentrationof hydrogen
results, was used to determine the operating conclltlons It I -(t.fi
for each
that give the concentrationofhydrogen peroxide ! IlI=0.('

stageof the vacuum distillation' I l{"1=il.5

l l{{=0..1
Models
Mathematical a l{i'(1..i

form
A secondorder polynomial which has the general
was employed in the range of the
fbr four variables, ii 1

indenendent variable, as represented by the following l

1
,.1 1 . I. 5 ( h f l
equation: l l = 0 1 (Jc r t l )
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+
+
,:l
+
BeXrX: + B7X1Xa+ B3X2X3+ BeX2Xa B 1 6 X 3 X a l
jr*---'1'-.''r
(1) I ll llr i(l l(l :Lr blr ;{} !1t jlrll lll

., :.: r ri X:r il. ,X,+ ii ,X:

\ 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

of Fig. (2) : Hydrogenperoxideconcentration
The effectof vacuumpressure on the concentration
the pressureat variousreflux ratios
hydrogenperoxidewas studiedin orderto determine
;i.;t;;d*hich
' distillationprocessis bestperformed' .li ---

that for all reflux ratiosstudiedthe

j
Figur. (2) show eil i \ tl=l.irlrrr
of hydrogen peroxide increases as the s :
'!
r 1-: ihr)
conJentration -\
at
vu"uut pressureincreases'Figure (2) shows that \!l
'r,
rl-,1.5 (hrl

R=0.3th; concentration ofhydrogen peroxide appearsro -i .\

r .l=lllrr)
sincethe ri ,.i,lrr,
i*u. ,fr. highestvalue but it is not desired' r
=- _-__o ..--.--
with water distilled is ---;---"''--* - -
arnountof hydrogenperoxidelost ':
i,il "-:If--
?

first stage
*u*l*ut. ttretJtort'ttte best reflux ratio for &.=-- r--=--..=-- -..-..-- -:l
-
: ii
'---l]=-.--
d i s t i-Ji"t"
llationwasfoundtobe(0.5-0.6)thisrangeofreflux 3iil
=" l _
r.ii" the desired concentrationof hydrogen Iltr.i -
a tl
r,t
'
peroxideandminimumloss' l l = ( r ((l f r l r)
of hydrogen peroxide in the water ii

The concentratton _ i { l1 -
--- T - --'

.jistilledisincreasedwhenthevacuumpressurelncreaseo I| lil
the best
unJ the reflux ratio decreased'Therefore Yrctltttlt l'rtrsttrt (ttttttllgI

conditionfbrconcentrationofhydrogenperoxidewas peroxide concentration vs' vacuum

foundto be in the vacuumpressure range(80-60mmHg) Fig.(3) : Hydrogen
stageand at varloustlmes
fo, ir.rt stage,the (60-40mmHg) for second Pressure
(30-20mmHg)for thirdstage' Effectof RefluxRatio
the concentration of
The vacuumpressureini'luences C:
hyarog"n p.ro*id, in different ways'
mainly the The effect of reflux ratio on the concentration
tille c:
operationat low pressureis normallyused
to avoid the nyarog.n peroxideat a given (vacuum.pressure'
(76 wt'o/oHzOz Oistillition),is shownin Figures(5) and (6)'
i'J.rnution of explosivevaporcomposition
andabove)andieavingUeiina the organic impurities'

2007)
IJCPEVol.BNo.3(SePtember

tIi -
Concentrati on of hydrogenperoxide by batch v Qcuumdistil!!\9!_

Examiningthese Figures it can be seen that the li ';'-- -

hydrogen peroxide concentration increases with s r:l
decreasing the reflux ratio. For exampleat R=0.3 the
concentration of hydrogenperoxidewasthe highest,but -li
i
it is not desiredfor first and secondstagesof vacuum l
.:
I'i
distillation, becausethe concentrationof hydrogen l
I
('{l .l
peroxidelostin thedistillatewateris maximum. I
l
Therefore theoptimumrefluxratioin first stageis (0.5- 1
l
0.6) and in secondstage(0.4-0.5).But in the third stage :01
optimum reflux ratio is (0.4-0.3) for limited the ti Jl
j .---.-a-.---,-*-_-
concentrationof hydrogenperoxide in distillate water .lt I
1 l l = 6 1 () r r I ) _. --. a

usingpackingheightof (80 cm).Refeningto Figure(4), li 1__

which clearly illustratesthat the lossesof hydrogen 1r.: lt.l ili {rfi 0: rrli

peroxidein the waterdistillateincreasewhenthe reflux l{rllur llrtirr

ratiodecrease. vs.reflux
Fig.(6) : Hydrogenperoxideconcentration
Thebestrefluxratiois theratiowhichgivesthedesired
ratioat varioustimes
concentrationof hydrogen peroxide product and
minimumloss.
' ri
'l j 1 . . I - I i r ( l( r l t r llrl '
l)
. | ,j r p l = l i l )t r r r r l l l _ t
I l1t t
. 4 . J r . l - t , {l)r l r r r
p { = 1 ( il r n r n l l l ) ..- ,-a-"'
.'\r .
1 r j = l l l( r r t n tllg ) . - , a - - - l
..i-' -
..4
' ''
- ,a-
-t' "',,.a''
..---
-,1-'.-.-.--''
,--J'
'd....
li -{1.5
l l = ( ) l l{ U r ) )

l s
_ _-_ -=- j
lr.0
l.:: 0..15 0.15 0.r5
vs.timeat
Fig.(7) : Hydrogenperoxideconcentration
R r f l u rl l ; r t i o
variousvacuumPressures
in water
Fig.(a) Hydrogenperoxideconcentration
distillatevs.refluxratio
Effectof Timeof Distillation
The best time of distillationis an importantfactor
1 . . I ' . . l { l l ll t t t t t t l l :
affectingthe concentration of hydrogenperoxide,which
t , l ' - S ( l{ n r r n l l ! t
a
r ' . . l ' = ( ' 1 i1n 1 ! r l l : l l must be known to avoid the rise of concentration of
1 . . l ' l t l ( n r n lrl i i impuritiesin thehydrogen peroxide product
to hazardous
l. l' .,:ll lrttrtrll'll
I
level.
t.
Sincetheprocess of distillationis batchwise,therefore
\ '-l-
therateof evaporation so thal
) it is essentialto determine
\ '
the time requiredshouldbe just sufficientto evaporate
about80-90%ofthe originalfeed'
r.'i.51hr) ExaminingFigures(7) and (8) it can be seenthat the
I | . , 0 (llc n r l concentrationof hydrogen peroxide increaseswith
increasing thetimeof distillation.
1t.i 1 r l. lt I \ It is clear from those Figuresthat when time oi
llrlltrr I{:rtirt distillationis equal(2.5hr) theconcentration ofhydrogen
peroxideis highest.But the product was not stable'
Fig. (5) : Hydrogen peroxide concentration vs' reflux alongwith the productand
b"causeimpuritiesevaporated
ratio at various vacuum Pressures
theamountof residuewasvery little (3-5 ml) out of (10(t
ml) is originallyfed. But when time was (l'5 hr) the

16 IJCPEVol.BNo.3(SePtember
2007)
amountof residue(10-15ml) andtheproductwasstable areaof distillationcolurnnpacking,,then it follows tb*
thereforethe best distillation time which leads to a high surface areas result in high heat and materid-
desired concentrationof hydrogen peroxideis greatly tansfer, Maximum efficiencyis obtainedby using lutg
dependentorirthe specificconditionsof the experiment columnsof highsurfacearea)161.
(i.e., amount of hydrogenperoxide,vacuum pressure' Thesefigures show also that for first and secondstage
temperature). 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)'
\ ttr=o,s Sincethe feed to this stageis relativelyhigh (75 wt'7o)
\tu=o.o
\ n:=n.r andto avoidbxcessive lossesofhydrogenperoxidein the
\ Hr=o.t water distillate and to achievethe desiredconcentration
\ tts=tt.l
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
P=li(l rDnrll{.1
flectricallyheatingthe column)t7].
l l = ( r l l( e n t )

\lt t* -*- '-----

0.: lt.6 1.0 l.l l.l{ l.l) '\

p l = l l X ){ r l r n l l g )
'I'inrclhr).
\ p 1 = 8 {l ln r n r l l g l
:u \ p . 1 = 6l0m n r l l g )
vs,time at
Fig. (S) : Hydrogenperoxideconcentration \ p J = { 0( r n n r l l g )
variousreflux ratios sr. \ p 5 = 2 0( n r r l l l g )

ffi
t IrlJ

':
9.:
:i t u
tt.: irs
::.5 \ : JIJ

J O : .tl
i
-:.: jil

.:1.5 0 :tr .lr| {ili lt0 ll}0

\. l)atking I'ltighl ( cnt )

t 1
Fig. (10) : Hydrogenperoxideconcentationvs. packing
r , i.l

v t.r'1 heightat variousvacuumpressures

. " i \-,-"----.-*-*,t
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 .n l ' = { 1 0( n r n r H g )
Fig, (9) : Hydrogenperoxideconcentration in water t = 1 . 5( h r )
distillatevs. Packingheight S-r

3ri \
Effectof PackingHeigrht
The effect of packing height is clearly observedby . ii

concentration hydrogen peroxidein water distillate'

Examiningflg*t (9), it can be seenthat increasing
packing tre'igbt"will decreasethe concentrationof
irydrogen peroxidein thewaterdistillate'
-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
dependsupon its ability to transfer ht* *9 material heightat variousreflux ratios
beiweenthe liquid and vapor sueams'Since,in the case
ofpackedcolumn,this transfertakesplaceon the surface

IJCPEVol.8No.3(September
2007)
Concentration ofhydrogen peroxide by batch vacuum distillation

Gonclusions Nomenclature
The following conclusionscould be drawn from this H PackingHeight. m
investigation:
P VacuumPressure. mmHg
l-The secondorderpolynomialregressionanalysisof the
objectivefunction i.e., the concentrationof hydrogen R RefluxRatio.
peroxide and four variables (i.e., vacuum pressure,
t Time. hr
reflux ratio, time of distillation,and packingheight),
for eachstagesof distillationwerefound. Y Calculated Value of the Response
2-lt is necessaryto concentratehydrogenperoxideby (Concentration
of HzOz).
using vacuum distillation in two or three stages
because:
a-Decreaseof the boiling point of hydrogenperoxide References
leads to decreasethe rate of decompositionof I'Green Wood N. N. EarnShowA., "Chemistryof the
hydrogenperoxide. Elements",John Wily.and Sons Inc., New York,
b-Obtaining hydrogen peroxide with high purtty and (1e98).
goodstability. 2-DavisS.N., KeefeH. J.,"Ind.Eng.Chem.",Vol.48,P.
3-The concentrationof hydrogen peroxide increases 745,(t956).
with: 3-Hampel A. Clifford, "The Encyclopedia of
a- Increasingthe vacuumpressure. EIectr ochemistry", (1964).
b- Decreasing the reflux ratio. 4-Kajiwara,et al, U. S. Patent,5, 534, 238, July, 9,
c- Increasingthetime of distillation. (19e6).
d- Increasingthe packingheight. 5-Ledon,et al, U. S. Patent,6, 187, 189,February,13,
4-The bestoperatingconditionsto concentrate hydrogen (2001),and U. S. Patent,6, 183, 638, February,6,
peroxideare: (2001).
a- First stage: 6-SkidmarR., "QyF TeachingSystem",ComingLimited,
i- Vacuumpressure(80-60mmHg). (1986).
ii. Refluxratio(0.5-0.6). 7-Kerl 8., "Hand Book of Laboratory Distillation",
iii- Timeof distillation(l.5 hr). ElsevierScientificPublishingCompany, (1982).
iv- Packingheight(60 cm). 8-GiguereP. A., "Cand.J. Chem.",Vol. 32, P, 117,
b- Secondstage: (l 9s4).
i- Vacuumpressure(60-40mmHg).
ii- Refluxratio(0.4-0.5).
iii- Timeof distillation(1.5hr).
iv- Packingheight (60 cm).
c- Third stage:
i- Vacuumpressure(30-20mmHg).
ii- Refluxratio (0.3-0.4).
iii- Timeof distillation(1.5hr).
iv- Packingheight(680 cm).

18 IJCPEVol.8No.3(September
2007)