Synthesis of Polyol 2013

20'nRegionalSymposiumon ChemicalEngineering(RSCE20t 3)
NoventberI2-13,2013
Alona Kew White Beqch Resort"Bohol, Philippines

REFERENCE NO. : B14
SYNTHESIS OF POLYOL FROM EDIBLE OIL WASTE
WITH OZONOLYSIS TECHNOLOGY
Aloysius Yuli W.; Lie Hwa
Department of Chentical Engineering, University of Surabaya
Jl. Raya Kalirungkut Surabaya 60293, East Asia, Indonesia
Ema i I : al oy_s ius1w GDs
t alf. ubaya.ac.i d

Abstract
Polyol is a chernicalcompoundthat containsmany hydroxyl groups.Polyol can be made from
petroleum,neverthelesspetroleum'sprice is increasinglyhigh ancl petroleum itself is a ltonrenewableresource,so it rnay be gone someday.Alternatively,synthesisof polyol can use other
materialthat is renewable,in caseit can usewastefrornedibleoil.
In experiment,polyol is made liom edible oil waste(usedpalm cooking oil) throughozonolysis
reaction.Besideozone,as reactantare also useda mixtureof rnethanol,isopropanoland water in
certainratio and sulphuricacid as catalyst.Mechanismof reactionwill startat ozoneattackand
breakthe doublebonds(C:C) of unsaturated

fatty acid in the waste,and then hydroxyl groupsof
alcoholcan madecontactto producepolyol.
The rnain purposeof experimentis to deterrninethe optimum conditionfbr rnakingpolyol rvith
ozonolysistechnology.The experimentwill be carried out by vary temperatureof ozonolysis
reaction,mol ratio of oil-alcohol,reactiontime and ozoneconcentratiorr.
TIre restrltof experimentshow that hydroxyl numbervaluesof polyol vary frorn 92.'I5ro 265.62
and viscosity values vary from 9.228 to 20.403 cp. The optirnum condition deterrninedby
responseoptimizationprogralx, and from experirnentshow that convertingedible oil waste to
p o l y o lw i l l b e e f f l c i e n tw i t h t e m p e r a t u r2e5 ' 1 , 3 h o u r sr e a c t i o nt i m e , l : 7 f o r o i l a n d a l c o h o lm o l
ratio and ozoneconcentration6.3 Yo.
I(eyrvords:polyol, ozonolysis,hydroxyl nurnber,viscosity

20't'RegionalSymposiunton ChemicalEngineering(RSCE2013)
l{ovember12-13,2013
Alona Kew White Beach Resort, Bohol, Philippines

INTRODUCTION
Polyol is a carbohydratebut it is not sugar,
polyol is a derived product of sugar. At this
time, the use of polyol increase,more than as a

raw lnaterial of polyurethane,as a synthesis
sweeter,and tlie caloric value of polyol smaller
than sugar,and it can reducedrespouinsulin to
sugar and becauseof the reason there is a
statement"polyol is a sugar free". Otherwise,
polyol is also as raw materialfor productionof
foarn.But at this year,total of polyol production
in the regionalmarketis very low.
Other materialto yield polyol is petroleurn,but
now the price of petroleurnis high and beside
that petroleum is non-renewable natural
resoLlrce, so it may be gone someday.
Alternatively,syntlresisof polyol can use other
material that is renewable,in case it can use
waste from edible oil. Synthesispolyol from
edible oil waste really can make improvement
the use of itself. The synthesis througlt
ozonolysisreaction,which is in this reaction
ozoue (O:) have cracked double bonds of unsaturatedfatty acid (oleatacid, and linoleatacid)
in the waste.At the next step, hydroxyl groups

(OH-) in the alcohol mixture merge with the
singlebondsC-C to producethe polyol.
Objectifs
l. Prodr"rcingpolyol from used palm
cookingoil witli the ozonolysisreactiou.
2. Find the optimumconditionto produce
polyolfrom usedpalmcookingoil.

MATERIALS AND METHODS
Materials
Materialswas usedin this research
are usedpalm
cookingoil, alcoholmixtureconsistof l0"h methanol
99%,800/oisopropanol
and l0% water,sulfuricacid
96%oas catalyst.Ozonewas generated
from oxygen
gaswith purity 99.5yothroughozonegenerator.Kl,
MgSOa
anhydrate,

KOH,HCl, andacetate
anhydrate.
Methods

Prior to the ozonolysis reaction,used
palm oil was analyzedfor its fatty acid content.
The experirnentalmethod for this reactionis as
follows: A mixture of Lrsedpalm cooking oil,
alcohol mixture (10% methanol, 80%
isopropanol, 10o water) and sLrlfuric acid
catalyst is added into a stainlesssteel reactor
equipped with cooling/lieatingsystem, stirrer,
tube spargerand therrnocouple.
The molar ratio
of methanolto usedpalrn cookingoil is varied
according to the experimentaldesign. Ozone
was produced from oxygen gas using ozoue
generator.The exit port of the ozonegeneratoris
connectedwith deep tube and the mixture of
ozone and oxygen gases is delivered to the

reactorthrough tr-rbespargerat the bottom. The
reactoroLrtletis connectedto a potassir-rrn
iodide
solution trap hence excess ozone will be
decomposed.The reaction was run at several
isothermal conditions and at certain reactiorr
times. After ozonolysisreaction,tlte generator
was turned off and the productof reactionwas
then flushed for about l0 minr-rtes
with oxygen
gasto removeozolteexcess.Followingthis,the
reaction product was allowed to attain roorn
temperature
and then neutralizedusiug sodium
carbonatesolution.The solutiouis then decanted
into a separatorfunnel then warnr water was
addedto attainpH neutral.
The resulted product was then dried
with magnesium sLrlfateanhydrous and then
filtered. The polyol product was then analyzed

for hydroxyl nurnber, alkali number, and
viscosity.
The experirnentwill be conductby the variables
ternperature,reaction tirne, ratio used pahn
c o o k i n go i l t o a l c o h o (l 1 : 3 ; 1 : 4 ; 1 : 5 ; 1 : 6 ; 1 : 7 ) ,
and ozoneconcentration.
Experimental Design
This researchfocusedon the effect of
four independentvariables ternperatr-rre
(X7),
reactiontirne (X2), molar ratio of oil to alcohol
mixtures(d), ozone corrcentration
(X), and on
responsevariablesof hydroxyl nurnberof polyol
product(f). The centralvalue of independent
variableswas used is temperatureof reaction

20"' RegionalSymposiumon ChemicalEngineering(RSCE20131
Noventber12-13,2013
Alona Kew WhiteBeach Resort,Bohol, Philippines

25oC;reactiontime 3 hours;molar ratio of oil to
alcohol mixtures I :5; and ozone concentratiott
5.8% rnol. Four independentvariables were
studied and optimized in the form of coded
value X, ,X2,X3,and Xo at five levels(-2, -1,
0, 1, 2) usingequation:
xo
x ,, = x i AX,
whereX,

is coded value of

independent

is real value of

independent

variable, xi

Synthesisof polyol with ozonolysisreaction.
In the experiment,synthesispolyol took place
through ozonolysisreaction.Mechanisrnof the
reaction is starled by ozone (Or) attackedand
fatty acid
crackeddouble bonds in un-saturated
(oleatand Iinoleat)in usedcookingoil.
+ o,r)
cH3(cH2)7cH:cH(cH2)7cooH
(oleicacid-double
bond)
cH.,(cH2)7cH-cH(cH2)7cooH
(oleicacid-single
bond)

variable
variable,xn is real value of independent
at central point, and Lx, is interval. The
distributionof coded values Xt,X2,X3,

arrd

in Table I .
X, as described
Table I
and Level Variable
Variables
Rdn$edah.lbvef
cod{-{
:2,; -:1 ,,4 :1,:, 2
value
Temperature("C)
Reactiontime (h)
Molar ratio

xl

Co.nn"

A1

x-

x3

15 20 25 30 35
t2345
l:3 1:4 l:5 l:6 l:7
4.8 5.3 5.8 6.36.8

+ Or )
CHr(CH2)1CH:CHCH2CH:CH(CH2)7COOH

(linoleicacid-double
bond)
cHr(cH2)4cH-cHCH2CH-CH(CH2)7COOH

(linoleicacid-single
bond)

After the severance of double bonds. the
hydroxyl groups (-OH) in the alcohol mixture
attachto C-C singlebond to forrnedpolyol.
+ CIITOH + C:H;OH+ H:O
H](CH,)?CH-CH(CI-I,)?C]OOII
(oleicacid-singlebond)
(rnethanol) (isopropanol)

RESULTS AND DISCUSSIONS

I

+

Tlre characterizationof used palm
cooking oil using Gas Chromatographyshows
variousfatty acidscontentas describedin Table
2.
Tablb 2
Fatty Acid Composition of Used Cooking Oil
Safurated fatty acid

(wt oh)
Composition

L a u r i ca c i d

1.78

Myristicacid

1.80

Palmiticacid

39.1

Stearicacid

4.42

fatty acid
Urrsaturated
O l e i ca c i d

36.6

L i n o l e i ca c i d

12.2

cH,(cH2)7cH(oH)-cH(oH)(cH2)7cooH
(polyol)

CHr(CH2)4CH-CHCH2CH-CH(CHr+
) 7CCIO
HH
HO
TO
(methanol)
( l i n o l e i ca c i d - s i n g lbeo n d )
+ CTHTOH
+ H2C)
(isopropanol)

I

I
V

cH,(cH,)tcH(orJ)-cH(oH)cH,cH(oH)-cH(oH
)(cH:)rcooH
(polyol)

20"' RegionalSynryosiumon ChemicalEngineering(RSCE2013)
NoventberI2-13, 2013
Alona Kew WhiteBeach Resort,Bohol, Philippines
At the observation,the reaction to produced
polyol was showed under change of colour of
solution.
At beginning,the Lrsedcookirrgoil appearedas a
browr.rcolour. After ozonolysisfor 2 hours,the
colour haschangedto brown pale as appearedat
figure 3. If the reactionwould have continued
for 4 hours,tlre colour would have changedto
browner pale. The change of colour was au
indicationthat the reactionsbetweenused palm
cooking oil and alcohol mixture have formed
polyol.
Hydroxyl Number
Hydroxyl numbersrefers to nurnberof
hydroxyl groups (-OH) in the chemical
compound.The reactionbetweenpolyol and diisosianatforrnedpolyurethaneas raw rnaterialof
foam.One of parameters
to classifiedpolyol in a
good quality is dependon the hydroxyl number,
it meanshiglrerhydroxylnumber,the qualityis
better because polyol witli higher hydroxyl
nuurber could easier fonned cross link witlr
diisosianatto yields polyol. Base on the data,
hydroxyl nurnberis a irnportantpararneter
to be
analyzed.The values of hydroxyl numbersof
polyolis shownas follow:
Table 3.
H roxil number rf nol
Time vol
Temp,
latio
Obser (nourl
, i?c)

.*t"rJ

vation

X2

xj

2
4
2
4
2

'4

6
7

4

:4

2

:6

8

4

:o

9

2
4
2

:4
:4

A

:o

2

:4
4

2
3
4

)

0
2
3

+

A

:4

:6
:o
:4

:6

5

2

.o

t)

I

:6

7
at

5

:)
)

&

xi

4.8
4.8
4.8
4.8
5.8
5.8
5.8
5.8
4.8

20
20
20
20
20
20
20
20
30
30
30
30
30
30
30
3L)
25
25

4.u
4.8
4.8
5.8
5.8
5.8
5.8
5.3
5.3

:t,,.::..:..r
r,.ltI

Hydrqksil.
,,Number
183.3181
233.3141
l 8 5 . 31 2 9
236.3312
255.0111
257.8537
262.t751
265.62t4

r5.0608
I 9 . 5 9 I3
27.65t3
27.9513
26.9793
29.08'75
27.0233
29.537|
30 . 3 6 8 2

5 3 . 8r08

l9
20
2l
22
L-)

24
25
26
2"7
28
29
30

3
3
3
3
3
3
3
3
3
l

3
3

3
:7

5
5

:)
:5
5
:5
5
r5

5.3
5.3

25

3 9 . 05r0

z5

+. -)

25
25
l5

51. 6 9 1 0
37.4228
57.6109
45.8878
92.7497
42.2484
43.4061
4t.7285
43.4208
12.8178
42.t902

o.J

5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.3

25
25
25
25
25
25

Frorn table 3 above, it is known that hydroxyl
numberwoLrldincreasedby the tirne of reactiolt,
for example : from the data nurnber 1 and 2,
hydroxyl numberof polyol prodLrced
in reaction
tirne 4 hours higlier than hydroxyl nurnberof
polyof producedin reactiontine 2 hours.The
resultscan be explainedas follow: longertirne
of reactioncausedcontactbetweenusedcooking
oil arrdalcoholin the reactoris moreintenseand
so moreamountof polyolproduced.
In table 3, it is also known that increase
of ozone concentratiou caused increase of
hydroxylnumber.Ozonecoltcentratiorr
givesan
effectto conversionof used palm cookirrgoil.
Ozoneis a reagentthat promotethe severance
of
double bonds C:C at unsaturatedfatty acid in
used cooking oil. Higher ozone concentration,
more amount of the severanceof double bonds
C:C unsaturatedfatty acid, so ntore antountof
hydroxyl grolrps (-OH) in alcohol rnixture
insertedand attachedto single bonds C-C to
formed a polyol. For exarnple,it is shown irr
observationnumber I and 5, the data have
shown that raisingozoneconcentratiollprolnote
raisingof hydroxylnumberof polyol .
For the telnperature,the use of higher
temperatureof reactiongave a significanteffect
to hydroxyl nurnbertoo. At high ternperature,
alcoholmixtureswill be vaporizedand as result
amount of alcohol mixture reactedwith used
palrncookingoil decreased
and polyol product
from the reactionhas a lower hydroxyl number.
Other reasonwhy hydroxyl nurnber of polyol
decreased at high temperature is at high
temperature
solubilityof ozone is small. Upon
the dataobservation
rrur.nber
9 until nurnberl6
(for ternperatr-rre
30 oC), hydroxyl number at

20"' RegionulSyntposiuntctnChemicalEngineering(RSCE2013)
12-13,2013
Jttovember
Kew
WhiteBeachResort,Bohol, Philippines
Alona
thesevariablesis lower than hydroxyl numberat
other data observation.At the data observation
nurnber 24 (for temperature35 oC), hydroxyl
number at these conditions is lowest than
hydroxyl number at other data observation.At
lower temperature,solubility of ozone in used
palm cooking oil went up and so ozone
concentrationin oil phasewent up too, and as
couseqLleuce
rateof reactionto yield polyol will
increase.For this reasonwhy hydroxyl number
of reaction l5 oC, 20
of polyol at temperatures
oC, and 25 oC more than hydroxyl number
polyol at othertemperatures
of reactionas 30 oC
a n d3 5 o C .
At table 3, it is shown that raising of
mol ratio betweenused palm cooking oil and
alcohol mixtures promote raising of hydroxyl
r.rr,rrnber.
The phenornenoncould be explained
if
rnol
ratio oil phase-alcoholmixturesrose,
that
total of mol esterpolyol increasedtoo. At higher
concentrationof alcohol mixtures consist of
methanol,isopropanoland water, the reaction
between used palm cooking oil
alcohol
mixtureswill producespolyolwith characteristic
h i gherhydroxylnurnber.
The experiment has produced polyol
witlr hydroxyl nurnber in tlre range 92.75 265.62.The highesthydroxylnumberis reached
at condition:reactiontirne4 hours,rnol ratio oil
phase-alcohol
mixturesI :6. ozoneconcentration
ok
5.8 andternperature
of reaction20'C. By the
statistictest (responseoptimization),optirnurn
point is in condition:reactiontime 3 jam, rnol
ratio oil phase- alcoholmixtures | : 7, ozone
concentration
6.3 o/o,and temperatureof reactiou
oC.
25
Atthis point,the hydroxylnumberis220.

range 9.228 cp - 20.403 cp. The highest
viscosityis reachedat condition:reactiontime 4
hours,mol ratio oil phase- alcohol1: 6, ozone
concentration4.8o/oand temperatureof reaction
30 "C. Further,the viscositywill influencedthe
characteristicproduct of polyLrrethaneif the
processwill be continued.When the polyol is
viscous,so it will forrnedrigid foam, and in the
other condition when the polyol has lower
viscosity,so it will formedflexiblefoarn.
This is the valueof viscosityof polyolat several
conditions:
Table 4.
Viscosity of polyol from experiment
ktio
.Ti*.. Mol
Reactant
Xr

,'4

4

-t

2

:o

4

+

:6

5

I

o

4

'.4

7

2

8

4

9

2

:o
:6
'.4

U
I

4

:4

2

'.6

2
3
4
5
6
7
8
9
20

4

:o

1l

L-)

24
25
26
27
28
29
30

2

/l

2

'.4
'.6

+

:6

1

5
3
3
3
3
3
3
3
3
3
3
3
3

Temp.
iuc)

Viscosity
(cn)

Xt

2
2
3

22

Viscosity
There are several factor inflr"rencedthe
viscosity of polyol prodr-rct,one of thern is
molecularweight. The productsof polyol in
experimenthave the differencecharacteristicin
hydroxyl number, the difference of hydroxyl
ruumberrnade the difference of structure of
molecules,
and as resultthe rnolecularweight is
also difference. Tlre difference of molecular
weight influencedthe viscosity of product.
Polyol from experirnenthave viscosity in the

(o/o) [O3]

{nou_rI

:5
:5
3
:7
:5

)
:5

)
:5
5

:)

4.8
4.8
4.8
4.8
5.8
5.8
5.8
5.8
48
4.8
4.8
4.8
5.8
5.8
5.8
5.8
5.3
5.3
5.3
5.3
4.8
6.3
5.3
5.3
5.3
5.3
5.3
5.3
5.3
5.3

20
20
20
20
20
20
20
2Q

30
30
l0
30
30
30
l0
30

14.7012
t7.t446
8.4704
l5.5l5tr
10.7510
12.7057
9.5701)
3 .l 5 3 7
I . 3 2 I1
tt.0405
3.92'74
20.4025
5 5075
4.9048
2.2985
8 . 32 5 6

3.235r
25
25
25
25
25
l5
35
25
25
25
25
25

9.0586

0.2623
4 . t 7t 7
3.0'/22
4.9048
6.1373
9.2279
4.6604
5 .I 0 8 4
4.456ft
4.49'7
5
4 . 4I 6 l
4.4161

In order to make clear the correlationbetween
variablesof the experiment
to hydroxylnutnber,

20't'RegionalSymposiunton ChemicalEngineering(RSCE2013)
NovemberI2-13,2013
Alona Kew WhiteBeach Resort,Bohol, Philippines
it is shown the figure 2i figure 3; and figLrre4
below.

w
ye

vt zw
tffi

(x1)and tirne
Figure2. The effectof ternperature
of reaction(x2)to hydroxyl nurnber

t4'

Yt

tffj

tw
s"t)

(x1) and mol
FigLrre3. The effectof temperatLrre
(x2)
nurnber
to
hydroxyl
ratio-reactant

vt

zffi

,w
,4

x1

Figure 4. The effect of terrperature(x1) and
(xa)to hydroxyl nurnber
ozoneconcentration
From the figures above, it is showlr that
hydroxylnurnberis increasingly
by the tirneof
reactior.r,ozone concentratiorr,arrd rnol ratio
betweerr
oil phase- alcohol,and as otherresult
is decreasinglyby
shown that hydroxyl nr"rmber
highertemperatureof reaction.The inforrnatiort
explanation.
is the samewith the previor.rs

CONCLUSIONS
l. At the conditionis as below:lougertirne
of reaction,higher ozoue concentration,
lower ternperatrrreof reaction, and
higher rnol ratio between used palrn
cooking oil-alcohol mixtures, the
hvdroxvlnurnberwill increased.
2 . Polyol from the experiment have
hydroxyl number is in the range of
9 2 . 1 5- 2 6 5 . 6 2 . T h e h i g h e sot f h y d r o x y l
r.rurnber
is reachedat conditiorr:reactior.r
tirne 4 hours. mol ratio used palrn
cooking oil - alcohol mixturesl:6,
ozone concentration 5.8 %, and
temperature of reaction 20 oC. The
optimumresultis in condition:reactior-r
tirne 3 hours, rnol ratio used palm
cookingoil-alcoholmixtures1: 7, ozone
of
concentration6.3 Yo.and temperature
oC.
hydroxyl
reaction25
The optirnurn
numberis 220.
3 . Polyol from the experiment have
viscosity is in the range of 9.228 20.403 cp. The highest viscosity is

20't'RegionalSymposiumon ChemicalEngineering(RSCE2013)
I\tovemberI2- I 3, 2013
Alona Kew WhiteBeach Resort,Bohol, Philippines
reached at condition: reactiorrtime 4
hours,mol ratio usedpalm cookingoilalcohol
mixtures
l:6,
ozone
concentration4.8 o/oand temperatureof
reaction30 "C.

ACKNOWLEDGEMENTS
Firstly, the authors would like to
acknowledgefor the financial supporl provided
by ResearchGrant frorn IndonesianDirectorate
Generalof Higher Education.Secondly,special
thanks to Lieke Riadi and Edy Purwanto for
lrardwork and supportas a team memberfor this
project.

REFERBNCE
l. Benecke,H.P.,B.R.Vijayendran,D.B.
Garbark,K.P. Mitchell, (2008), "Low
Cost and Highly Reactive Biobased
Polyols:A Co-Productof the E,rnerging
BiorefineryEconomy",Clean-Air,
Soil,
WaterJournal,36, 694-699.
2. Ong, Y.K. and S. Bhatia.2010, "The
Current Status and Perspective of
Biofuel Production via Catalytic
Cracking of Edible and Non-Edible
O i l s " ,E n e r g y3, 5 , I I l - l I B .
3. Petrovic, Zoran, Guo, Andrew, Javni,
Ivan,"Processfor The Preparationof
Vegetable Oil Based Polyol and
ElectroirrsulatingCasting Compounds
Created from Vegetable Oil Based
Polyol", Pittsburg State University,
2003.
4. Tran, Graiver, Ramani, "OzoneMediated Polyol Synthesis frorn
SoybeanOil", Departmentof Chemical
Engineering and Material Science,
M ichiganStateUn iversity.
5. Krischenbauer,
1960,"Fat and Oil. An
Outline of Their Chemistry and
Technology", Reinhold Publishing
Co..NewYork.
6. Criegee, R., 1915, "Mechanism of
Ozonolysis".Angew.Chem.lnt.Ed.Engl.,
14.145-752.

7 . Ketaren,Oil and Fat,Jakafta,University
of Indonesia,1996
8 . Fessenden &
Fessende."Orsanic
Chemistry",3'r'edition,jilid l, Ja[arta:
E r l a n g g al ,9 9 l .