The Effects of Molar Ratio of Glycerol 80% and Palm Oleic Acid on the Synthesis Process of Ester Glycerol

TABLE OF CONTENT S

In nova tive Agroindustrial a nd Business System E ngineering

Thc Feasibility Study of Establishment of Biodiesel And Paving Block I- I

Industry From Spent Bleaching Earth

Febriani Purba, An.i Suryani and Sukardi

Green Supply Chain Management Innovation Diffusion in Crumb Rubber 1-7

Factories: Designing Strategies towards Implementation

Tri Susanto, Marimin Marimin and Suprihatin

Mobile Business Analytics System for Service Level Analysis of Customer 1- 13

Relationship Decision

Taufik Djama and Yudhistira Chandra 8ayu

Exploring an lnnovative Approach to Address Non-Tariff Barriers 1- 19

Experienced by Small to Medium Enterprises in Downstream Coffee

Production in Indonesia

Andar Hennawan, Yandra Arkeman. Titi Candra Sunani

An

Analys is of innovation Network Performance on the Palm Oil Industry 1-26

in North Sumatera

Danang Krisna Yudha, Aji Hennawan and Machfud

Exploring the Internationalization Process Model of an Indonesian Product 1-33

- C:lse study: Fruit Chips SME's

Dickie Sulistya Apriliyanto. Hartrisari Hardjomidjojo. Titi C Sunarti

Innovation Management in Indonesian Palm Oil Industry

1-39

Karim Abdullah. Aji Hcnnawan and Yandra Arkeman

Technology Innovation Adoption to Improve the Pcrfomlanee of Dairy 1-45

Small-Medium Enterprises (SME): Case study in Pangalcngan-Bandung

Regency, West Java, Indonesia

Nuni Novita."ari. Titi Candm Sunarti and Nastiti Siwi Indrasti

Managing Innovation through Knowledge Sharing in An Indonesia Coconut 1-54

SME

Muchammad Kodiyat P. Maebfud, Nastiti S Indrasti

Increasing Added Value of Banana by Producing Synbiotic Banana "Sale"

1-60

Using Innovation

&

Technology Strategy Approach

Eka Ruriani

An

AHP Application for Selecting A Business Innovation Strategy of 1-65

Chocolate SMEs in East Java

Yani Kanika Pcniwi, M. Syamsul Maarif and Maehfud

Understanding local food consumers and their motivations: A case srudy in 1-71

Padang city

Poppy Arsil

Spatial Model Design for Competitive Improvement of Small Medium 1-77

Scales Enterprises (Case Study: Boger Area)

Hanrisari Hardjomidj ojo. Harry Im:mtho and Armaiki Yusmur

System Analysis and Design for

ｓｾｬ･｣ｴｩｮｧ＠

Chitin and Chilosan Industry

1-82

Location

by

Using Comparative Performance Index Method

Dena Sismaraini. Naslili S. Indrasti and Taufik Djatna

Arduino-Based Tempcrature

Monitoring

Device

for

Cold Chain 1-90

Delmar Zakaria Firdaus and Endang Warsiki

Devdopment of Downstream Cocoa Industry: Exploring the Role of f-95

Govemment and Small and Medium Industry in Partnership

Farda Eka Kusumawardana, Yandra Arkeman,

Titi C

Sunarti

The Role ofComnmnicarion in the T ccnnology Transfer Process

1- 101

Anindita Dibyono. Sukardi , Machfud

The Center for Pulp and Paper Appraising its Productivity

III

Generating

1-108

Industry-Applicable Research: A Good Practice Illustration

Ahmad Rudh Firdausi. Anas

M

Fauzi. Machfud

Frontier Approaches in Process and Bioprocess Engineering

Identification of Flavor Compounds In Ccmcem

(Spondia=pinata

(LF)

11- 1

Kurz) Leaf Extra

Luh Putu Wrasiati.

Ni

Made Wartini and Ni

Putu

Eny Sulistyadewi

Synthesis and characterization of nanosilica

from

boiler ash with co-

11-5

precipitation mcthod

Wahyu

K.

Setiawan, Nastiti S. Indr3.sti , and Suprihatin

The Comparison Of Media on the Microalgae

Nanllochloropsis

sp . Culture

11 - 10

Anak Agung Made Dewi Anggreni.

I

Wayan Amata

and I B

Wayan

Gunam

Identification

of

Media and Indicator Liquid as A Recorder Sman Label

11·14

Endang Warsiki and Riris Octaviasari

The EfTects of Palm Oil MES Surfactant and Inorganic Salt Concentration

1I- 19

on Interfacial Tension Values

RisHl Fitria, Ani $uryani. Mira Rivai and Ari Imam

Effect ofNano Zinc Oxide On Characteristic Bionanocornpositc

Tt-25

Siti Agustina, Nastiti Siswi Indrasti. Suprihmin and Numl Taufiqu

Rohman

The Effects of Molar Ratio Between

80%

Glycerol And Palm Oil Acid on

11-3 I

the Synthesis Process of Ester Glycerol

Mira Rivai. Erliza Hambali, Giovanni Nurpratiwi Putri . Ani Suryani.

Pudji Permadi, Bonar T.H Marbun and Ari Imam Sutamo

Selecting Part of Natural Fiber EFB which has Best Mcchanical Strength 11-37

through Tensile Test Analysis for Composite Reinforced Matcrial

Farkhan, Yohancs Aris Purwamo. Erliza Hambal i and Wawan

Hcnnawan

Idcntification of phenol rcd as Staphylococcus aureus indicator label

JI ·44

MC'lati Pratama. Endang Warsiki and Liesbetini Hartoto

Enhancing Ethanol Tolerant of

Escherichia coli

Recombinant

by

Glutamate

11 -48

Addition under Aerobic Conditions

lndra Kurniawan Saputra, Prayoga Suryadanna and Ari Pennana

PUlra

In

Vitro Potentifal

of Antibacterial

Marine Microalgae

EXlract

II -53

Chaetocero:!!J{racilis

Toward

Staphylococcus epidermidis

Bacteria

Ardhi

Novrialdi

Ginting. Licsbctini

Haditjaroko and

Iriani

Setyaningsih

The

Potential Applications of

Modified

Nagara Bcan Flour through II-59

Susi. Lya Agustina and Chondra Wibowo

Studies on thc Chamctcristics

of

Pasayu (Pasca

of

Waslc-Cassava)

11-64

Fortification as a New Product Development

Marleen Sunyoto. Roni Kastaman. Tati Nurmala and Dedi Muh tadi

Optical And Particle

Size

Properties Of

Sargassllm

Sp Chlorophyll As

Dye-

TI-72

Sensitized Solar Cell (DSSC)

Makkulawu Andi Ridwan and Erliza Noor

Alkaline Pre-Treatment of

Gelidium

tari/oliulII

and

Caulerpa racemosa

for tI-76

Bioethanol Production

Dwi Setyaningsih.

Neli

Muna, Elisabeth Van Vivi Aryanti and

Anastasya Hidayat

New Trcnd$ in Industrial Environmental Engineering

&

M:magement

Usc of Biofiltcr to Improve Quality of Polluted River Water fo r Drinking

1JI- 1

Water Supply

Suprihatin , Muhammad Romli and Mohamad Yani

An Empirieallnvesrigation of the Barriers to Grecn Practices in Yogyakart3

IIl -8

Leather Tanning SMEs

Dwi Ningsih. Ono Supamo, Suprihatin and Noel Lindsay

Preliminary Study For CO

2

Monitoring System

III- IS

Farhan Syakir, Rindra Wish, [rvi Firqotul Aini, Wisnu latmiko and

Ari Wibisono

Designing a Collaboration Form to Overcome Innovation Resistance in

TJI-22

Waste Managemcnt Practices in Lampung Tapioca Industry

NUT Aini Adinda. Suprihatin. Nasli!i Siswi Indrasti

Pollution Reducing Opportunities for

a

Natural Rubber Processing Industry: III-29

A Case Study

Sya rifa Arum Kusumastuti. Suprihatin and Nastiti Siswi Indrasti

Effects of Palm-Dca Non-Ionic Surfactant as an Additive in Buprofezin

111-35

Insecticide on the Efficacy of it in Controlling Brown Planthoppcr Rice Pest

Fifin

Ni.syu.

Rahmini. Mira Rivai. Nobel Cristian Siregar, Ari Tmam

Sutanto and Ainun Nurkania

Intelligent Information

&

Communication Technology

for

Adaptive

Agroindustry of the Future

Design of Web-Based Information System With Green House Gas Analysis IV- I

fo r Pa lm Oil Biodiesel Agroindustry

Yandra Arkeman. Hafizd Adityo Utomo and Dhani S. Wibawa

Sequential Pattems for Hotspots Occurence Based Weather Data using

IV-8

Clospan algorithm

Tria Agustina and Imas S. Sitanggang

How to Dcal with Diversity in Cultivation Practices using Scenario IV - 13

Generation Techniques: Lessons from Ihe Asian rice

LeI

Initiative

Kiyotada Hayashi. Yandra Arkeman. Elmcr Bautisla, Marlia Mohd

Hanafiah. long Sik Lee. Masanori Saito. Dhalll Satria, Kaiehi

Shobatakc. Suprihatin, Tien Tran Minh and Van Vu

Vila D Ldyana. Erwinsyah and Kiyotada Hayashi

Scquenrial Pattern Mining on Hotspot Data using PrcfixSpan Algorithm

IV-20

Nida Zakiya Nurulhaq and Imas S. Sitanggang

An Intelligent Optimization Model Analysis and Design of Bio-filtration in

N-24

Raw Water Quality Improvement

Ramiza lauda and Taufik Djatna

Development Of People Food Consumtion Patterns Infonnatiol1 System IV-30

Based On Wcbmobile Application.

fadly Maulana Shiddicq, Rani Kastaman and Irfim Ardiansah

Association Rules Mining on Forest Fires Data using FP-Growth and IV-37

ECLAT Algorithm

Nuke Ariney and Imas

S.

Sitanggang

Development Of Expert System For Selecting Tomato

(S(){anllm

IV-41

ｾｹ｣ｯｰ･ｲｳｩ｣ｯｮ＠

L.)

Varieties

Erlin Callya

Rizki

Amanda. Kudang Bora Seminar. Muhamad Syukur

and Noguchi Ryozo

Developing Life Cycle Inventories for Rice Production Systems in IV-47

Philippines: How to Establish Site-specific Data within

the

General

Framework

Elmer Bautista, Kiyotada Hayashi and Masanori Saito

Con!>truction of Site-specific Life Cycle lnventories for Rice Production IV-50

Systems in Vietnam

Tran Minh Tien , Bui Hai An, Vu ThiKhanh Van and Kiyotada

Hayashi

Study on Life Cycle Benefit Assessment as a tool for promoting thc solution iV-53

of Environmental Problems

Tetsuo Nishi

Real Time Monitoring Glycerol Esterification Process with Mid IR Sensors IV-57

using Support Vector Mach ine Classification

Iwan Aang Soenandi. Taufik Djatna, Irzaman Husein and Ani Suryani

Extrdction of Multi-Dimensional Research Knowledge Model from IV-63

Scicmific Articles for Technology Monitoring

Arif R. Hakim and Taufik Djatna

Perfonnance of Artificial Lighting Using Genetics Algorithms

IV-69

Limbran SampebalU

The Application of Fuzzy-Neuro Approach for ERP System Selection: Case IV-74

Study on an Agro-industrial Enterprise

ICAIA 2015 ISBN: 978·1-4673· 7405·7

The Effects of Molar Ratio of Glycerol 80% and Palm

Oleic Acid on the Synthesis Process of Ester Glycerol

Mir.J. Rivai. Erliza Hambali. Giovalmi Nurpratiwi Putri. Ani Suryani. Pudji Pcmladi,

Bonar Tua HaJumoan Marbun. Ari Imam Sutanto

SUifactaw ami Bio<'lIergy Research Cellfer. Bogol' Agricllflural Unil'ersi!y

Fac:u /ry of Agricultural Technology. Bogor AgricullUral UI/h'ersil),

Program Study of Petroleum Engineering. Bandw lg InSlilllle o/Techl/ ology

£·mail:

m .. _rar;vai@yahoo.cnm.erliza.h@gmail.com. gio\·anninllrprariwi@gmail.com.

anisUlJ'ani.sbrc@gmail. com, pudji@,lm.itb.ac.id. bollar.marhun@yahoo.com, ari_imam@)·olzoo.com

AbslraCl--Glycc rol este r was 5"ynlbesizL-d b y

I.'slerificalion of glycerol and pulm oleic ucid usiuJ!

methyl ester sulfonic acid (MESA) as catalyst. The purpose of Ihis study was to obtain the bl'St mola r

ratio in the esterification of 80% glycerol with

palm oleic acid using 0.5% MESA catalyst.

Gl ycerol 80-/. was esterified by using a nitrogen

stream at J80°C and a stirring speed of 400 rpm for 90 minutes. ｒｾｳｵｬｴｳ＠ sho wed thlllt ｴｨｾ＠ best molar ntio wus 0.8 : I (glycerol: olek acid) which produced glycerol heer with the yield of 75.33%,

density of 0938 g1cm). acid ｮｵｭｬｮｾｲ＠ or 39 ml KOH/g sample, viscosity va lue of 92 eP (30·C), kinema tic viscosit), of 53 cSt (40°C), flash point a t 204°C. pou r point a t O°C. and boiling point al 105°C.

I. I"<TRODU(IION

G

LYC EROL cstcr can be synthesized through an

esterification process by reacting glycerol with carboxylic aeid and catalyst. This ｰｲｯ｣･ｾ＠ produces water as a by-product. Esterification is a revcn;ible process !'oo Ih:l.t one of the reactants needs 10 be priorly fed in order to push the reaction 10 the right side or to

product formation. A catalyst is used to avoid the need of high tempera ture, longer reaction time. and Ihe formation of dark--colored product [18].

Manu,..ripl r«civcd April 29. 201 S. This work w:u supported

m ｾ＠ of fac,hucs from Surf:u:lam ;ml.l Buxncrgy Rescan:h

Ccnll.T·8oti:or Aj;I1eultund Un, ... -n;II), (SBR C IPS) and fil\llIKC

front I . .cmbag:l Ａ＾ｾｮｧ､ｯｬＮＮ＠ Dana Pcn.hd,kan {LPO?) wc«"

ｈ｣ｫｾｬ｣､ｧ･､ Ｎ＠ ｔｨｾ＠ Eft"e(:1S of Molar Ratio or" Glycerol 80"10 and

Palm ｏｬｾＬ･＠ ,\eld on the Synthesis Pruo;ess ofE-<l1.T Glyea-ol

Mira Ri\"ai is with Suri:.eunl &nd BiocnC1"ji;y ReseJJ\'h Cenla".

Bogar Agrieuhurnl UnivCl".<;oly ﾫＨＮＢｏ＼ｔｾｾｮ､Ｌｮｧ＠ author 10 provide

cm;ul: ml: ｲ｡ｲｩＬＮＢ ｾｮＩＧ＾ｬ ｨｯｯＮ｣ＬＬＬＢＩ＠

ErI,za Hamb:.h is ""th Tlcpartment of ａｧＺｲ ｯＢＬ､ｵＮｾｭ｡ｬ＠

T«hnology. Faculty of .... gncultur.<l TechnolOi,Y, SogO!

ａｬＺｾＺｮ･ｵｬｴｵｲ｡ｬ＠ Un,versity Md Surfactant Ind B,o .. :ncrg) R<!SI..'3rch

Cellia-. Bo!:(lI" Agnculrurnl Uni"cysn) (email: crlil!:l.Mi.gmiIJl.com)

liandayani et til. [5] slated (hat reactant-catalyst ratio was one of the factoN: afTec.ting reaction effectiveness. In the esterification of glycerol with oleic acid. thc molar ratio of glycerol to oleic acid reactam is an important factor to observe. In this study, the esteritication was done with glycerol 80%: oleic acid reactant ratios of 0.8:1: 1.7:1: and 2.6:1.

Methyl estcr sulfonic acid 0.5% was used as a catalyst.

II. PROCEDURE

A. Purification ofGlyceml as a By-product of Biodi/!sei Production

Glycerol purification was dont by using a purification reactor of 25 L scale. The purificalion device is shown in Figure 1.

G,o\'anm Nulpl1lu"," Putri

,<

w,th D':partmcnt of ａｧｲｯｭ､ｵｾｬｮ｡ｬ＠

Tc-chnology. Fncuh)' of Agricullurnl ｔ｣｣ｨｮｯｬｾＧｙＮ＠ Bo!:OI"

As:riculwral Uni,'eI"S'ty (email: .\:,o,·anni"urpl1l1iwi@ ｉｉｭｾｩ＠ I.com j.

Am Suryani ,s with Ikpanmenl of AlVumdustriaJ T""hnolOi!Y.

Faculty of Agricullur.iI T«hnolug)'. Bogar Agncultund Un,vcrs,ty

and ｓｵｲｦ｡｣ ｬ ｡ｮｾ＠ and BiocUCfgy ｒ｣ｾ｡ｮＺｨ＠ Center. BOj;Qf Agncultural

Umn ... ny (em:,,!: 3n15ur)",ni.$brtC" iffi3it.com).

Pud;: t'a-n\ad, IS ＢＧＺｾ＠ I'"rogram Stu:.!y of PC1rol:um Enginern"o.

Dandullg InSI;!ull: of T«hnolul:}' and Surfactant and ｂｩＢＧＢｾＧｾＢｦｬＺｙ＠

R=rch Center. ｂｯｾｯｲ＠ Agncultural Un,vcn;lty (email:

pud) ｉ ｾｌ ＢＢＺｬＮ［ｬ｢ Ｎ｡ ｣ＮＬ､ ＩＮ＠

Bon;::- Tu;\ Halumo.:m Maroun i, wilh ｐｲｯｾｲｾｭ＠ Study Qf

P(u<.>leum F..nlj,U1""T"'g. JUndung In.<litule of Technology (c:maiL

bonlU .m.mun("yuhoo.com).

Atl lm;un SUlllIllO ｪｾ＠ with Surfaclanl and ｂｩｯ｣ｬＱ･ｲｾＧｙ＠ Research

Center. Bogar Agricuhurnl Um vtnily (enlail:

:m_'m:un{" yahoo.com)

ICAIA 2015

•

- -

-'"

Compo<ln11 of punfic3tion ""'tor

I. l'unlic(ltion tank 6. _{ｲｲＮｬｬｮｾｷｯｲｫ＠} ofpancl

2. Cap unk 7. ｗｨｾ｣ｉ＠

3. ｅｬｾＧ｜ｃｴｲｩ｣＠ mOlor K Unit holdcr

.l . Entr)' funf'ci

S. Control pane:!

9. Cook.:r unit 10. Output

Figure I . Design of purification rcactor of 25 L scale Glycerol purifielltion pro(';cl>l> was dono.: under a condition process used by [151 with some moditications. Firs!. crude glycerol. a by-product of biodiescl industry. '.vas placed in a purification lank and heated until the temperature reached 50°C. Then. 85% technical grade phosphoric acid was added in by

5"to (vlv). the temperature was raised to 80°C. The

mixture was heated and stirred for 4 hours before it

W:lS left for 30 minutes until thrce layers were fomlcd. from lOp to bottom. the three layers consisted of free fany acid. glycerol (product of purification). and !rolt. Glycerol and sail were taken out from the purification lank before they were scpar.lted by using a filti.ltion device.

B. esterification of Purijie(1 Glycerol

In thIS synthesis of glycerol done through esterification. glycerol resulted from the purification was reacted with oleic acid in molar ratios (glycerol:oleic acid) orO.8:1, 1.7:1. and 2.6:1 ｜｜ｾｴｨ＠ an addition of MESA catalyst (w/w) by 0.3°/0. The esterification was conducted in lriple neck nash put on hol plates at 180°C for 90 minutes. During the esterification process. nitrogen was flown into the flasks at the rate of 100 mUminules to avoid the exislI:ncc of oxygen and push Ihe formed WOller vapor OUlto Ibe condenser.

C. Allalyses of ｇｾｶ｣｣ｲｯｬＮ＠ MESA Catalyst. and

G(vcerof El·ter

Analysis of glycerol. MESA catalyst. and glycerol

ISBN : 978- 1-4673-7405-7

estcr were done to mcasure glyecrol content. density (OMA 4500M AnIon Paar). viscosity (Brookfield DV-111 ultra), pH. acid number. kinematic viscosity (ASTM D 445). boiling point (ASTM 0 86). flash point (ASTM 0 92). and pour point (ASTM 097).

D. Drl/(J Analysis

A factorial complclc!y nmdomiz..:d design with two replicates was used. Thc faclOT was MESA catalyst

｣ｯｮ･ｾｮｴｲ｡ｴｩｯｮ＠ (A). The experimental dcsign model

was:

( I)

where:

Y,!I Observation valuc as alTcctcd by factor A at

i-level jJ '" Mcan value

A, '" Effect ofmol:l.r ratio atj-Icvc1

0 ..

0.8:1; 1.7:1;

2.0J)

1:" Error of experimental unit al i-level of facior A

and J-Ievc1 of replicate U- l.2)

Data were subjected to analysis of variance by using SPSS 16.0 progr.lm and a Duncan test at a s

5%. The te.<:t was done to measure inter-level diO'erences in a factor.

Ill. RESULTANDDlSCUSS10N

A. Physiccx:hemical Properties

oj

Purified Glycerol

Crude glycerol was purified by the addition of 85% phosphoric acid by 5% (v/v). The acid reacted with the remains of potassium hydrochloridc catalyst to fonn a potassium phosphate salt and (II Ihe samc timc

scparate free ftlfty acids. The remaining methanol, which did nOi rcact. evaporated when glycerol waS healed at 65°C. The result was 80% purt: glycerol having different physicochemical properties from those of crude glyccrol. Thesc differences are shown

III T "hie I. l'urifiCUlion ｰｲｯ｣･ｳｾ＠ mercased glycerol

\\!vel. lowered viscosity and demit), levels. and brightened the color.

TABLEt

PHVSICOCHl:.MICAL PROPERTIES OF CRUDE AKO PURIFtEO GL VCEROL

ｐｍｬｕｬｬｉＮＱＮｾｔ＠ Unit Crude _glyc<:rOl l'urifil'li _{g!yco::rol ｳｬｹｲｾＡﾷ＠}

""re

!.l:vel or

''-glycerol 45 .t 2.05 lI4 io 2.00 I ｯｯｯＬ ｾ＠

ｖｩｾｯｳｬｬｹ＠ at _,p

30' C 625"'1.07

189:0:0.70

1 ""

Dcnsiry al

J&.cmJ 1.0745 io I 2S76 :t 1.261

2S ' C 0.0001 00001

C.""

Blackish Hro" .. msh No color

｢ｾｮ＠ y.:Ilow

RoIhng

·C

_{1\0 io 3.25 1I2 :t. 2.05 29'}

I!£im

• [7). [D]

[image:7.594.77.273.85.361.2]

lCAIA 2015

B. Physicochemical Properlies of ME5"A ｃｕｉｕｾｉＧｳｴ＠

MESA (melhyi es/er sulfonic acid) is an intcnnediate compound resulted from the sulphonation reaction of

methyl

eSler. It

is

dark colored and acidic. Thc propcrtics of MESA in this scudy arc sho",;n

in

Table 2. Bascd on its pH v:Jlue, MESA is ｾｴｲｯｮｧｬｹ＠

acidic. This spt:cific property of MESA has bee n the basis of its use as cat::llysl in esterification. As in other acidic catalysts. the acidity of MESA is suspected to rcsull in the protonation of oleic Dcid which is the initiation of estt."r fommtion process.

lABLE 2

?HYSTC'OCHEM1('AL PRorr;RTIFS OJ' MESA CATALYST

Parameter

pH ('''/ 0 in dislilled ""ncr)

IXnsil)';ll 2S·C C"""

Unll Value

ＲＮｾ＠ f. 0.20

!:'c ml 0.917310.0001

Black

C. Ph)Wi"ocilemico/ ｐｲｯｰ･ｲｴ ｩｴｾ＠ nfGlycerni £t/er

Esterification is the fonnation of ester by rcacting fatty acid with alcohol. Glycerol ester is an ester whose alcohol molecule is glycerol. As the esterification result, i'.\'0 layers arc formed. The top

layer is glycerol ester and the bottom layer is the remaining glycerol which does not react. In this study, thc rcsulted glycerol ester was a mlxturc of monooleic. diolelc, and triolelc glycerols and thc remaining fatty acids whi..:h did not rca..:t.

According to (16]. in order to get optimum product, the reaction balance of estcrification should be ptl.ilhed to (he right position or produe( formation by supplying energy 10 thc fc-actlon. ovcrfcedlng the reaCianlS, and continuous removal of product during the process Esterification process is a reversible reaction so that it is necessary to maintain the direction of the process to the pru<luction side. In this study, this was done by overfceding glycerol reactant to the reaction. The formation of two layers in the esterification product was cau:.ed by the finding thnt in the end of the reaction there was some glycerol which did not get reacted. During the esteritication proces!', nitrogen gas was continuously flown into the flask to push the water vapor out of the flask. As wate r vapor was a by· product of estcrific':!lion, the removal of it would le.ld to an optimal glyecrol estcr production. If it was not removed out from the reactor, the fomlcd .... ';ltef vapor might hydrolyze glycerol ester back to glycerol and oleic aeld. The yield and the physicochemical properties including add number. density. viscosity, kinematic viscosity. flash point, pour point. and boiling point of glycerol ester produced were measured .

I) Y,eld

In this study. yield was the amount of glycerol reacted with oleic acid to result in glycerol ester. It is shown in Figure 2 that wider molar ratios resulted in fewer yieldS. This indicaled that overfeeding of

ISBN: 978· 1-4673· 7405·7

glycerol, under the esterification condition used in this study. did not result in higher glycerol ester yield. This might be caused by the fact thai the purity level of glyc!;rol wa.iI only 84% so that when it was overfed to the esterification process. more filth was found in the esterification material. These filths inhibited the tbm\ation process of glycerol

ester.

Estt..-rifiC;J.tion done with higher amount of oleic acid (molar ratio of 0.8: I) resulted in high yidd. Thi:-. indicated that higher amount of oleic aeid fed in the esterification process increased the possibllity of the fonnalion of estcr bonds between glycerol and olcic acid.

'00

m ' OJ

l

ｾ＠

,

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ｾｾ＠

ｾ＠ ｾ Ｇ ｟ｯ｡＠

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0.1:1 1. ' 1 ｾ ＮＶＺＱ＠

FIgure ｾ｟＠ Etkt:15 of mol:ll" ratio on glycerol ｣ｳｾ｣ｲ＠ }ldd

It was also sho\\.'I1 that molar r.ltio factor did not gi\'c sib'Tlifieam cOect (p>O.OS) on Yield. It was suggcsted therefore that a molar ratio of 0.8: I be used

\0 gct high yield of glycerol ester. 2) pH

The glyccrol ester sample taken from the c!\tcrification W'dS a mixture of Illonooleic. diokie, lrioleic ｧｬｹ｣ｾｲｯｬｳＬ＠ remaining oleic acid which did not react, and MESA catalyst. pH measurement was done by dissolving glyecrol ester in 30% distilled water. It

W:J!» found that ｾｉｹ｣｣ｲｯｬ＠ estcr samplc did not dissol ve in the water but MESA catalyst did. pH measurcmtnt was taken to assess the .lmount of MESA catalyst found in thc ｾＧｓｴｾＧｲｩｬｩ｣｡ｴｩｯｮ＠ product. Highe r pH level indicated hig.lter anlount of MESA catalyst found in glycerol ;;sler. ResulLiI of pH measurement arc depicted in Figure 3.

SO

6.0

ｾ Ｍｴｏ＠

2..0

00

5.46 5.-5 6.11

0.8:1 1.- :\ ｾ ＮＶＺＱ＠

:"lolar ratio (glycerol : oleic acid)

ｆｩｾｵｲｾ＠ 3. ｅｦｦｾｬ＾＠ ormobr ratio on piT

It is shown in Figure 3 that a widcr molar ratio or higher amount of glycerol fed illto esterification led to lower pH levels. This was eaused by the find ing that the pH levcl of glycerol ester fonned WIIS in line with

[image:8.594.314.495.577.677.2]

ICAfA 2015

thc pH le"eI of glycerol. In this study. purified glyccrol had a pH Icvel of6.24.

3) Dellsit)'

Density or specific gravity is a weight of a liquid per unit volume. Density measurement was taken [0 assess

Ihc: imeT-llIolc!eu\c denscness in glyccrol eSier yielded.

It is shown in Figure 4 that glycerol ester with high density was yielded in wider molar ratios. According 10 [9]. the density It!vel of eSler of carboxylic fatty flcid was tlfl"i:ctcd by molccular weight and

temperature.. Highcr molecular weight mcant higher density level.

"

ｾ＠ I':: _0.938

0

.2i

0.9

ｏＮｑ Ｔｾ＠ 0.943

i'Q.6

ｾ＠ 0.3

0.0

O.S.1 1. - ' 1 '::.6:1

[image:9.611.88.276.241.343.2]

MOlar nllio ＨｧｉｙＧｾＱＢｏｉ＠ : ｯｬｾｩ｣＠ acid)

Figure 4. ｅｦｦ･｣Ａｾ＠ of molar ratio on drnsity level of g,lycerol n;u:r

It was found that molar ratio factor did not give significant effect on dcnsity [c'·cls. This might be

caused by the faci that each sample of esterification product contained similar main components. nam::!!y monooleic. dioleic. and trioleic glycerols. Therefore. the dcnsity level or each sample was nOI too different.

II was foulld th31 molar mlio r.,ctor did not glVI.' significant cfTect on dl.'nsity levels. This might be caused by the fact that each sample of e.m:rification product contained similar 111.1in components. nnmely monoolcic. diokie, and lrio!eic g!ycwols. Therefore. Ihe ､｣ｮｾｩｴｹ＠ level of each sample was nOI to() diffcrent.

4) Acid Numher

Acid number IS used to J.SSI.'SS Ihe amount of fatty acids per gram of sample. Highcr acidic number indicates higher amount of fatty acid coment. Acid numbcr shows how much (ml) KOH is nccded 10 neutralize ! gram of [aUoil. It is shown in Figure

5

that. in gcneral. an increase in molar ralio Il.'d to 3n increase in acid number. This meant that wider molar rJ.lio 'vas not followed by higher yield conversion to glycerol ester lea"ing fTl<)re fatty acid which did not react in the esterification process. As oleic aeid has an acid number of 200 mg KOHlg sample, high amount of oleic acid remains which did not react in Ihe process would lead to the production of glycerol ester \\ith high acid number.

[SBN : 978-!-4673-7405-7

,

0.8:1 _1.6:1

\101 ... rlUO I.b.-ervl

,ok"

":1(1)

Fig ... ", S. EffO;<:I$; ofmolu I":IUO on acid numba' Qf Slycerol C:Slcr

It was found In3t molar rmio f3ctor ga\ e significant etTl.'cts on acid number of glycerol eSler.

5) ViSCOSity

Viscosity is

a

physicm:hemical propcny showing the level of thickness of a fluid. An increase in viscosity is a result of increased molecule concentration [1

OJ.

Increased .... iscoslty of a material may also caused by increased chain length :l.nd molecular weight. Viscosity alTecls thc flowing characteristic of:l. fluid: higher viscosity me3ns lower capacity of the fluid to flow, As can be secn in Figure 6, higher amount of glycerol fed into the process led 10 widcr molar rJlio and higlll.'r viscosilY level. This

was attributed to thc faci that the vis.cosity of glycerol estcr yielded was always in line with Ihe viscosity of g[ycerol used. In addition, 35 discussed above, wider molar mIlO did nOI yield in higllcr amount of glyccro[ cster [caving morc oleic add which did not involve in the reaction. This. in tum, led to a higher viscosity levcl of glyccrol ester.

ｉｾ ｏ＠

c

"

0-

'"

"

..

,

.,

"

,

;:; ;0

0

0.8:1

lI!oLar I":I!IO <g l)urol . ｯｬ･ｩｾ＠ Icid)

ｆｩｬＡ｜ｬ ｲ ｾ＠ 6. ｆｲｲｾＧ｜ＡＱｓ＠ 01 molar milO on ｖｉｾｏｓｬｴｹ＠ teveh Qrgl)'\'c:rol .:ster.

II was revea!ed that, in general. glycero[ ester yielded from the molar rJlio of 0.8: 1 the lowest viscosity level. This indicated that must glycerol ester was produced in [he esterification proces.s done with a mol:l.r ratio of 0.8: I. This was supported by thc finding that molar ratio factor gave significant efTect on thc viSCOSity levels of glycerol ester.

6) }.,'ilJemut/c Viscm'ity

Kinematic viscosity is the measure of the resistance of glycerol ester to flow. Higher kinematic viscosity level means that it is more difficult for the subst3ncc to flow. According to [llj. tht.: value of kinematic viscosity is afTectcd by the length of carbon chain and thc position and number of doubl.: bonds of falty acid or alcohol used in an ester synthesis. Longer carbon chain means higher kinemalk viscosity level while

[image:9.611.309.491.454.537.2]

leAIA 2015

numbcr of double bonds has a negative relation with kinematic viscm:ity level. Kinematic viscosity is a func tion of dynamic viscosity and de ns ity: inc reased kinematic viscosilY is resulted from hight.-r dynamic viscosity and lower density le vel (8]. In this scudy, it WllS rcvcllled Ih:1I wider molar mtios gave higher kinematic viscosity level which was in line '>I.11h viscosity level (Figure 7).

r:

I "

1

0

•

i y ... ... i.P)_. _ O<4l

ｆｩｾｲｴＢ＠ 7. Efli.,<;tS of molar r.1I10 un kinematic viKOSiry of

ｧｬ Ｉ ｾｴＺｲｵｬ＠ Cl>lcr

Molar ratio was found 10 give no :.ignificant ･ｦｦ･ｃｌｾ＠

on kinematic viscosity levels (If yielded glycerol ester. As disc ussed abo\'C, esterification of glycerol and oleic acid rcsullcd

in

glycerol ester in the fonn<> uf monoolein, dioldn , or trIOlein. One of th em was found to be dominant and :lfiect their general physicochemic:ll properties. This non-significant difference suggesled that all samplcs share eoounOD main components in relatively similar concentration.

i) Flash Poi,,1

Flash point is the lowest temperaturc at which a <:.ubstanee starts 10 ignite and bum itself II] . It is a parameter ::Iffected by the eOnlent of volatile tractions (alcohol residue). Accordi ng to [1 2]. higher content of \'olalilc ｦｲＮｬ･ｬｩｯｮＮｾ＠ in an ester nukes it need onlv low temperature to ignite. A material wilh low flash'point is easier to get burnt and therefore needs special handling and storing. In esterification. as an alcohol, glycerol releases its hydroxyl groups and binds oleic acid to fonn ester, This makes the flash point of glycerol ester higher. Purified glycerol and oleic acid have flash points of 120"C and 204"C. n;"spcclivcly. Rc1D.ti vc1y similar component compositions found In

samples make their flash points relatively the same.

8) Pour PO;nI

According to [4]. pour point is the lowes\ temperature at which a sample is still able 10 flow. Lower pour [X)int of a material indicates that the material is able to flow at low tempenllures. According to [14]. the chain length ::Ind unsalUr,lIion of a molecule affcci its pour point. Longer ehOlin length increases pour point while double bonds indicating unsaturntion lowers it. In this study, the pour poims of all glycerol ester ｾｭｰｬ･ｳ＠ were found to be tht: same, namely

O"c.

T his showed thai at tempemnlrcs below a ce. there would be white crystals f<)nlled in the glycerol ester fi nd it would no longer be

ISBN: 978- 1-4673-7405-7

able to flow, A fluid with low pour point is beller 10 be used m areas with low temperature.

9) Boiling Poin!

Boilillg point is a physicochemical properly showing a temperature at which a material starts to boil . Boiling point shows intermolecular force in a fluid: strongcr force means highcr boiling point. According to [6J, boiling poim is affected by molecular weight and th.: eXistence of hydrogen bonds. In this study. as shown in Figure

8.

boiling pointS of glycerol ester weTe slightly fluctuating . The highest boil ing point was shown by glycerol ester yidded from Ihe molar ratio of L7:1.

Ｌｾ＠

':: I!O

•

ｾ＠ <

•

ｾ＠

ｾ＠

ｾ＠

•

'"

"

,

,

.

,

｜ＱｶｉＮ＼ｲＢＢＢＧＡ ｾ ｴＺ＼Ｌ＠ .... ｾ＠ ...".· .... 11

ID '

: .0 I

Figure 8. Elfecl.'l o( mow r.ltio on boiling poont of gl}<;crol ester

It wus shown that molar ratiu gave significant effects (a .. 5%) on the boiling points of glycerol ester yielded. The boiJing points in molar ratios of 0.8: I and 2.6:1 were not different but they were significantly different from the boiling point of glycerol ester in molar ratio of 1.7: I. This was an indication that glycerol ester yielded in the molar r.l1io of 1. 7: I had the highest conccntration.

After the properties of glycerol ester were analyzed. the best esterification condition W::IS dctcnnined based (In the parameters of the analysis done, First, based on Ihc yield, the highcst yield of glycerol ester was obtained from molar ratio of 0.8:1. Density level was not included in the consideration as no s i!,'flificant cfTcct of molar ratio was found o n it. In addi tion. the difference in the density levels of glycerol estcr yielded in different molar ratios was negligible. The lowest acid number ｜｜ｾ｡ｳ＠ tound in glycerol ester yielded in molar r.Jtio (If 0.8: I. Further. glycerol ester in this molar ratio also had the small est viSCOSity and kinematic levels, Low ｶｬｾ｣ｯｳｩｴｹ＠ and kinematic viscosity levels indicated most pre ferred glycerol ester as it would be the easiest one to flow. The next parameter W'J.s flash point and the preferred glycerol ester W::IS the one \\;Ih highest flID;h point. A substance with high nash point is nOI easy to get burned making it easier \0 handle. As no significant difference was found ｦｬ｡Ｎｾｨ＠ points. glycerol es ter yielded in molar ratio of 0.8:! was then selected as the best. Similar consideration was given to pollr points which werc not signilicamly different making glycerol ester yielded in molar ratio of 0.8: I as the best. Finally. b(lsed on the boiling point. the beSl glycerol ester was thc one yielded in mo lar ratio of 1.7: I as it had the highest boi ling point. O"erall. it was decidcd thaI the best

[image:10.604.309.498.257.327.2]

ICA IA 2015

csterific;Jtion condition was thc one done in molar ratio of 0.8: I.

IV. CONCLUSIO:-"

The best esterification process was obtained in molar ra tio of 0.8:1. Glycerol ester produced in this condition had a yield of 75.33%, density le\'eI of 0.938 glcm3. acid number of 39 ml KOH/g sample.

viscosity of 92 cP (30°C). kincmatk viscosity of 53 cS! (40°C). flash point of 204°C. pour point of O°C. ;Jlld boiling point of t05 e

e.

Recotnt!lIdarion

It was suggcstcd that esterification of glycerol 80% \\ith palm oleic acid be done in molar ratios wider than 0.8: I.

ACKNOWLEOGME"''T

Supports of facilities from Surfactant and Biocnergy Research Center (SBRC IPB) and finance from Lemhugo Pengdola Dalla Pelldidikoll (LPDP)

were acknowledged.

REFERI!NCES

II! Am....-ican So<.:io:t) for TC"ling and \1&I<;ri;ils. ''SlOIntlard Tot \1elhods for Flash Poim by ｐｃｬ｢ｊ｣ｹﾷｍｬｬｮｾｳ＠ Closed Cup TeSler". ASTM. \Vasllingtoll DC. 2005.

[2J Ammcan Soci"'), for Teslmg and :>'iHteMals. "SIW1dard To::.!

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Washington DC, 2009.

[3} ａｭｾＮＮＭｩ｣｡ＮＧｬ＠ ｓｯ｣ＧｾＧｉＮｹ＠ for TCSl1ng:tnd Ｚ｜ｩｾｴｬ［Ｇ｜ＧＱ｡ｬｊ［Ｎ＠ "Si.)J1d:lrd ｔｾｬ＠

\iethods for ｋ［ｲＮＺｭｾｵｴ＠ ViiCOIuy IIf Tr:lnsp.:u;;n: ｾｮ､＠ ｾｬｉ･＠

l.'qu,ds". ASD.1 . W;r.shlllgion DC. 2009

14] Amc:riclin Society fill' Testin!: and Materials. Sland.,rd Test Method., for Pour J'Qml of Pctrolrum Product .... A.STM.

Wash,ngIO<l DC. 2009.

[5j A. ｬｉ｡ｬｬＮｊ［ｬｽＧＺｬＧｾｩＮ＠ S. Marsudi. M 1"a.<ikin. and ｾＱＮ＠ ｓｵ､ｬ｢ｾｾ､ｲｩＩＧｏＮ＠

I:.slc:nfic.:lhon ReacllDn of OleiC Acid ,tnd GI)'C<.WI ｕｾｭＮＺ＠

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Q.;100cr 2006. pp. 102· 105. ISSN. pp. 1411·109S

[61 C R. Kmn")'. A ＤＩＬＮｴｾｭ＠ ｾｉ｡ｵｮｧ＠ Iftokcular ｾｴｮＮｴ｣ｴｵｲ･＠ of

orpn,c ｣ｯｭｰｯｬｬｮ､ｾ＠ ... ｾｴｨ＠ thC1r bo,hna pII,nts. ｃｨ･ｊｭ･ｾＱ＠

LaboJrolOl)' Ulah UDl\·c:n;,ty. Salt L.ke Cny. "'051. 1938. [71 J. B Segur. iWd H.E. Obcrstar. Vi..:osity of ;;1)'tCTOI and it,

aqueous ｾｬｬｉｬｬｯｮｳＮ＠ f.ll,tt. Chem .. 43(9). 1951, pp. 217i·2120

[81 J.

c.

C . Hernandez ond D. E. P. ｃ｡ｬ｡ＱｾｮＬ＠ PmJictmg the kmematic \'i1'<:osny of FAMes ｾｮ､＠ blodl,<cl: ｾＧｔｔｉｰｩｲｩ｣｡Ｉ＠

modd:!.. fu(l, Journal 01 Fut! and En.::rgy. No. 7144. 0'.1. 2014

[9] 1. C Phillip .• and G. J. Manamal. ｆＮＡｔｾ｣ｴ＠ of number of

carboxyl grQp\lS on IlqU".! ､ｾｳｬｴｹ＠ (If e-;!eN or al1o:)1carboxyhc

IC'ds.

En,

Chern .. 23( I). ;97&. JlP. ] ·6.

[IOj K !lokmhcrw:.8 Jom",;"", B K,m1bcTlI , and B lmdman •.

ｓｵｲｦｾ｣ｴｮｮｵＺ＠ ii!1d Polymers. in ａｱｵｾＧｏｓ＠ Soluuon. Jhon Wiley &

Sons. lid .. lond()ft. 2002.

[11 J K. ｇｬＧｔｨｾｲ､＠ and K. R. Steidle)'. ｋｴｮｾＧＱｔｉｾｬｬ･＠ VbCOS'\Y of fall)'

acid methyl ･ｾｬ･ｦＡＧＺ＠ !'redicIIOll. ｣［ｴｬｾＱＮｬＱ｡Ｎｴ･ｩｪ＠ "i5COSlty

contribution of esters with una\'llil"bk data. and ca!bon

Ol)'gcn C'lUl'':llcnL", Fuet. tI4. lOll. pp. 321 ［ｾＳＲｾＴ＠

[12} M Mittelbach and c.:. Rcmschmidl. B,odie.'oCl. !SBN· ＳｾＲＰＰﾷ＠

002.19· 2.2004.

[I3J \1. P.gh31'\) an,J M. Ros..i. The FUIU"" orGJ)'CCfol New Uld

or

0 VCl1illl1k R.:tw ｍ［ｵｾＮＢ｡ＡＮ＠ The Ro)aJ Socio:ty ｯ ｦｃ ｢ＮＺｲｵｪｾｴｴｹ Ｎ＠

Cn",bridgc. 2006.

ISBN: 978- 1-4673-7405-7

[!4J N. U. Soriano. V.P. Jr. Migo. M. Matsumllra. 07DnlZN vcgetable oil as JWUr point depressant for ncat hlooiescl, Fuel. liS. 2006. JIll. 25·31.

[15J O. Famb,c. Utih,;tlloo of byprodutl GI}ccrot of B,od'e<cl I' roduccion as ａｵｾＮｨ｡ｲｹ＠ Material of ｃｾＧｉｔｬｭＨ＠ elUshe', 11 .. :sis. Hogill' Ag,iculloral tlni\'I:fSII)'. Bogor, lndones.a. 2009 [16J R. J. Fd>cndm and J.5. ｆｾ＾｣ｲｋｬﾢｬｬＬ＠ "Organ,!: Chemica]". Vol

2 (3). ｦｲｬｾｮｧｧｾＮ＠ ｊＳｫＮｭｾ＠ 1982.

[17] IndoneSia National Slandard. Crude Glyc.·rol. ＺＭＮＱＳＱｬＰｮｾＱ＠

Standardmul()lI Aseney 01 Indoncsta, };U.::ut:I. 1995. [181 Y. H Hui. Railey Ａｮ､ｵｾｴｲｩＮｬ＠ Oil and hi Products. Vol!. J

Wi1<:)'. i'lL"'" York. 1995.