Purification of a neutral pH crude glycerol from

biodiesel plant into high-purity glycerol using carbon

active adsorption, membrane filtration, and rotary
evaporation.
Keywords: Crude glycerol, high purity glycerol, purification, activated carbon, adsorption,
rotary evaporator, membrane

1. INTRODUCTION

pharmaceutical industries. Furthermore, it

Biodiesel is an alternative fuel

source which produces glycerol as their
byproducts and mainly generated by the
trans-esterification

of

animal

fats

or

vegetable oils with methanol in presence of

an alkali or acid catalyst.13 In recent years,
the biodiesel industry is growing rapidly so
there are large amounts of glycerol. 4
Glycerol from bio-diesel production is
usually called crude glycerol because there
are some impurities such as salt of fatty
acids and inorganic salts. Crude glycerol
typically contains less than 65% wt. glycerol
and has low value in commercial markets.

Purification of gly-cerol is an attempt to

increase the profits of biodiesel producers,
which produced high-purity glycerol that
has

higher

selling

price.

High-purity

glycerol finds wide use as an important

feedstock for various industrial applications
in

food,

cosmetic,

and

can

be

use

in

plastics,

resins,

and

cellophane.6
To upgrade the purity of glycerol, a
suitable series of purification procedure is
required. Because of variations in biodiesel
production methods, the composition of the
crude glycerol also varies widely. Owing to
the different compositions of various crude
glycerol

feedstocks,

crude

glycerol

purification procedure is also necessarily

different. A different procedure lead to
different result of purified products that can
be recovered.

711

For crude glycerol with an

alkaline pH, procedure begins with a

neutralization or acidification using certain
acids. Sulfuric, hydrochloric or phosphoric
acid are usually used to neutralize excess
alkaline catalysts.4,5,7,8,1015 Effects of acid
types in crude glycerol purification also has
been investigated.4

Manosak et al.10 deve-

loped a method to purify crude glycerol by

employing

three-step

procedure:

an

environment. The use of membranes for

acidification step, followed by polar solvent

glycerol

extraction, and activated carbon adsorption

unwanted impurities such as beta-carotene

step. The highest glycerol purity (99.7 wt.%)

pigment, the remainder of the activated

was obtained as the result of preceding

carbon adsorption processes, as well as

sequential

study

inorganic salts. Using a membranes is

performed crude glycerol purification by the

relatively new and offers some potential

sequence of

advantages such as ease of operation,

and

procedure.

water

Another

membrane filtration, solvent

evaporation,

and

purification

activated

robustness,

charcoal adsorption, produced the maximum

methods.12

glycerol content (97.5 wt.%).12

In

adsorption

and

are

to

efficiency

eliminate

over

other

In this work, we develop a procedure

activated

to upgrade a neutral pH crude glycerol from

carbon use as crude glycerol bleaching and

biodiesel plant into high-purity glycerol

decolorizing agents. Activated carbon has

(>90% wt.). The procedure are carbon active

large surface area and high porosity, it

adsorption, membrane filtration, and rotary

adsorbs pigments and organic matter easily

evaporation. Neutralization with acid that

for large glycerol samples.8 Adsorption

always included in any procedure of other

ability can be affected by several factors

experiment didnt include in this experiment

such as a concentration of adsorbent,

because initial pH of the sample is neutral,

adsorption time, and temperature adsorption.

not alkali. Besides purity level, purified

The greater the concentration of adsorbent,

product has the same specification with

the

glycerol in the commercial market. Crude

adsorption

process,

process

Adsorption

decreased

increasing

temperature.16

will

increase.

linearly

with

purified

glycerol

samples

were

to

characterized for the glycerol content,

evaporate water and solvent that has been

density, viscosity, and the presence of

trap

vacuum

different functional groups. The best of our

distillation or an evaporation using a rotary

knowledge, no systemic purification work

evaporator is a good choice.11 Furthermore,

has been conducted using a crude glycerol

membranes are widely applied in the textile

with neutral pH to produce high-purity

industry as a treatment for the color waste

glycerol.

in

glycerol

Meanwhile

and

samples,

they produce before discharge into the

2. MATERIALS AND METHODS

Materials

first stage is purification of crude glycerol

Crude glycerol was obtained from a

local biodiesel plant at Surabaya, Indonesia.
Periodic acid, sodium thiosulfate, potassium
iodide,

glacial

chloroform,

acetic

acid

potassium

(99,5%),
dichromate,

hydrochloric acid, potassium hydroxide,

ethyl alcohol (95%). U.S.S.D Formulas 30
or 3A, soluble starch, and powder activated
carbon were purchased from Kurniajaya
MuktiSentosa company. All chemicals are
reagent grade. Cellulose nitrate membrane
was

produced

Experiment consisted of two stages, the

in

Polymer

Laboratory

University of Surabaya and has 0,2 m pore.

Crude Glycerol Purification Procedure

and the second stage is characterization of

glycerol that has been through a series of
process in the first stage. The purification
stage only through three processes namely
adsorption, membrane and evaporation. In
adsorption

process,

we

used

powder

activated carbon with using one kind

variable. That one variable is adsorption
time (20, 40, 60, 80, 100, 120 minutes).
Characterization of glycerol purified done
qualitatively (analysis of functional groups)
and quantitative (glycerol content, density,
and viscosity).
1. Activated carbon adsorption
Six sample of crude glycerol in beaker
glass was treated by mixing it with powder
activated carbon (2%wt.) with constant
stirring for 30 minute at room temperature.
Then, the adsorption process was carried out
for 20, 40, 60, 80, 100, and 120 minutes.
Each sample has different adsorption time.
Sample result from adsorption was filtered
using a Buchner funnel that had been coated
with three layers of filter paper. Note: The
filtering process was performed three times
in order produce a free sample of activated
carbon and done with the aid of a vacuum
pump so filtration process go faster. Each

sample was filter diluted to 10% wt. by

temperature of the water bath (124C), and

adding 90 grams of water.

vacuum pressure (500 mmHg) is set. (From

table

2. Membrane filtration
Cellulose

nitrate

membrane

and

Wattman filter paper prepared in accordance

with the size of the membrane column.
Membrane and filter paper installed on the
bottom of the column membrane. Then, the
top of the third column and clamps fitted to
the inside of the airtight column. Some
distilled water put into a column, and the

at

Mayer-Bugstrom,Z.deut.Ol-Fett-

Ind.,44,417-418.1924) Process above is

carried out until no more droplets down to
the flask distillates. An in the end, samples
were characterized.
Crude and purified glycerol samples
were characterized in duplicate by the
parameters below, obtained by the methods
of analysis given:

column is connected to the compressor. The

(a) Glycerol content were determined by

airflow is opened slowly, so that water on

a Iodometric-Periodic Acid Method

the membrane column trickled out until

according

exhausted. Air flow is closed, and gently tap

on the top of the column membrane is

to

references

Official Method Ca 14-56).

(b) The
density was
determined
according to ASTM

opened.
3. Rotary evaporation
Rotary evaporation was performed using

(AOCS

(2004).
(c) Viscosity

was

measured

891-95
with

Brookfield viscometer for small

rotary evaporator equipment from Wilmad-

sample

Labglass, RV 10 digital type.

First, put

guide book or ASTM Standart

water in a water bath that exist on the

device. Samples glycerol results from

Method for Non-Newtonian fluid.

(d) Fourier transform infrared spectra

previous processes put in a round bottom

(FT-IR) were obtained using the KBr

flask. Round-bottom flask containing the

method on a Nicolet Magna-IR 560

sample and an empty round bottom flask to

spectrometer operating at 1 cm-1

collect the distillate is placed in the space

resolution in the 400-4000 cm-1

that provided. Button on the device is urged

region.

round-bottom flask containing the sample

immersed into a water bath which has been
filled

with

water.

Rotary

speed,

the

according

to

Brookfield

BIBLIOGRAPHY
1.

Demirbas, A. Comparison of transesterification methods for production of biodiesel from

vegetable oils and fats. Energy Convers. Manag. 49, 125130 (2008).

2.

Pinzi, S. et al. The ideal vegetable oil-based biodiesel composition: A review of social,
economical and technical implications. Energy and Fuels 23, 23252341 (2009).

3.

Keera, S. T., El Sabagh, S. M. & Taman, A. R. Transesterification of vegetable oil to

biodiesel fuel using alkaline catalyst. Fuel 90, 4247 (2011).

4.

Nanda, M., Yuan, Z. & Qin, W. Purification of crude glycerol using acidification: effects
of acid types and product characterization. Austin J. 1, 17 (2014).

5.

Xiao, Y., Xiao, G. & Varma, A. A universal procedure for crude glycerol purification from
different feedstocks in biodiesel production: Experimental and simulation study. in
Industrial and Engineering Chemistry Research 52, 1429114296 (2013).

6.

Christoph, R., Schmidt, B., Steinberner, U., Dilla, W. & Karinen, R. Glycerol. Ullmanns
Encycl. Ind. Chem. 6782 (1998). doi:10.1002/14356007.a12

7.

Kongjao, S., Damronglerd, S. & Hunsom, M. Purification of crude glycerol derived from
waste used-oil methyl ester plant. Korean J. Chem. Eng. 27, 944949 (2010).

8.

Wan Isahak, W. N. R., Che Ramli, Z. A., Ismail, M., Mohd Jahim, J. & Yarmo, M. A.
Recovery and Purification of Crude Glycerol from Vegetable Oil Transesterification. Sep.
Purif. Rev. 44, 250267 (2014).

9.

Hjek, M. & Skopal, F. Purification of the Glycerol Phase After Transesterification of

Vegetable Oils. 44th Int. Pet. Conf. Bratislava, Slovak Republic, Sept. 21-21, 2009 16
(2009).

10.

Manosak, R., Limpattayanate, S. & Hunsom, M. Sequential-refining of crude glycerol

derived from waste used-oil methyl ester plant via a combined process of chemical and
adsorption. Fuel Process. Technol. 92, 9299 (2011).

11.

Ooi, T. L., Yong, K. C., Dzulkefly, K., Wan Yunus, W. M. Z. & Hazimah, A. H. Crude
Glycerine Recovery From Glycerol Residue Waste From a Palm Kernel Oil Methyl Ester
Plant. J. Oil Palm Res. 13, 1622 (2001).

12.

Dhabhai, R., Ahmadifeijani, E., Dalai, A. K. & Reaney, M. Purification of crude glycerol
using a sequential physico-chemical treatment, membrane filtration, and activated
charcoal adsorption. Sep. Purif. Technol. 168, 101106 (2016).

13.

Yang, Y. M., Kim, K. J. & Lee, Y. Glycerol separation from biodiesel byproduct. J.
Korean Ind. Eng. Chem. 19, 690692 (2008).

14.

Sadhukhan, S. & Sarkar, U. Production of purified glycerol using sequential desalination

and extraction of crude glycerol obtained during trans-esterification of Crotalaria juncea
oil. Energy Convers. Manag. 118, 450458 (2016).

15.

Fan, X., Burton, R. & Zhou, Y. Glycerol (Byproduct of Biodiesel Production) as a Source
for Fuels and Chemicals - Mini Review. Open Fuels Energy Sci. J. 3, 1722 (2010).

16.

Oscik, J. s., Goworek, J. & Kusak, R. Adsorption of aliphatic alcohols from benzene
solutions on silica gel. J. Colloid Interface Sci. 79, 308312 (1981).