NEW METHOD OF PURIFICATION OF GLYCERIN FROM

BIODIESEL USING SILICA GEL AS ADSORBENT

J. Q. GALVÃO NETO1, F. B. ROSSATO2, T. T. VINHAL3, S. ELYASI4

1
Universidade Federal da Paraíba
2
Instituto Mauá de Tecnologia, Escola de Engenharia Mauá
3
Universidade de São Paulo, Escola de Engenharia de Lorena
4
Lakehead University, Canada

E-mail: joaodequeiroz@msn.com

ABSTRACT – Biodiesel is a well-known fuel from renewable resource. During the

production of biodiesel, glycerin is the main by-product. Considering the amount and
type of impurities in glycerin such as, water, methanol, and salt; it cannot be directly
used as a raw material. It should be refined. Traditionally, the raw glycerin undergoes a
purification method that uses vacuum distillation, which is an energy extensive and
complicated method. Purifying glycerine, we developed a new purification process that
runs at ambient temperature and pressure using silica gel as adsorbent being able to
achieve a concentration of +99% glycerin. The adsorption material can also be reused
over more than 50 cycles without losing its performance. For regeneration of sorbent,
low grade heat stream at low temperature (below 120 ⁰C) may be used. As a result, the
proposed purification technology is not complicated and can be easily designed and
integrated into existing biodiesel facilities with minimum modifications.

1. INTRODUCTION
Biodiesel as a biofuel is produced by a transesterification process using vegetable oils or animal
fats with methanol, frequently catalyzed using alkali reagents (e.g., sodium hydroxide and potassium
hydroxide (Saleh, 2010). Glycerin is the main by-product, 10% by weight of oil yields (Kongjao et
al., 2010), with low energy value considering the impurities. Crude glycerin is separated from
biodiesel layer after completion of transesterification reaction. The main impurities are salt, water,
soap, traces amount of methanol and esters.

Most researchers used conventional methods to purify glycerine (+99%) at high temperatures
and low pressure (vacuum) which will end up to high operating cost, for instance, using vacuum
distillation to obtain a high grade glycerine up to 99.5 weight percent (Carmona et al., 2009). Other
non-distillation methods were developed. Hajek et al. (2010) used saponification, neutralization and
filtration processes obtaining 86% glycerine. Kongjao et al. (2010) applied acidification,

neutralization, separation of the phases, and extraction of alcohol achieving glycerine purification up
to 93.3%. Moreover, some biodiesel producers use the glycerine by-product as fuel but when it is
combusted at high temperatures (200 – 300 ºC), releases harmful substances such as acrolein
(Steinmetz et al., 2013).

Glycerine is widely employed as raw material in many industries such as, pharmaceutical, food
and cosmetic industries (Thompson; He, 2006). However, the methods known lately to treat glycerine
show that the purification process is economically unfeasible. As a result, it is essential to find
economical feasible alternative for purification of this valuable by-product (Quispe et al., 2013).

In order to increase the utilization of glycerin, it is necessary to obtain glycerine with less
impure chemical substances and in a concentrated form. Further improvement in the use of the by-
product would affect positively the biodiesel production. Aiming to overcome the costs of
purification, it was developed a new method that purifies glycerin at ambient pressure and
temperature. This method uses compressed dry air sparging through raw glycerine to remove water
and alcohol. Air is dried using silica gel and returns back to the glycerine column through a close
loop system. Using this technique, glycerine with +99% could be obtained without using high
temperature and low pressure process.

Considering this method, some sorbents were tested, such as calcium chloride, silica gel, and
water-absorbing polymer known as water-gel crystal. Calcium chloride is a known desiccant with
high hygroscopic properties. Solid dry calcium chloride is converted to liquid after absorbing
moisture. This behavior it causes to be extremely difficult to handle and dry the desiccant. After
drying, it forms a solid layer which needs to be crushed to a proper size. As a result, calcium chloride
is not a proper sorbent for the purpose of this study. Water-gel crystal absorbs high quantities of
water, around two to four hundred times when compared to its original weight, but the mass transfer
is a barrier when compared to silica gel. It needs a long period of time to absorb water. In addition,
glycerin is absorbed to the water-gel crystal which reduces the total recovery of glycerin. Silica gel,
as non-corrosive chemical, has been selected due to its relatively high adsorption capacity, low level
energy consumption during the regeneration process (below 120 °C), easy to handle, and moderately
its low cost (Fang et al., 2014).

2. MATERIAL AND METHODS

2.1 Material
Pure glycerin (USP grade) with 99.5% purity was used. The main impurity in glycerin was
water. Orange indicating silica gel desiccant was purchased from local Canadian supplier. The silica
gel was in the form of small sphere with uniform size of 3 mm. Producing raw glycerin, edible canola
oil was reacted with anhydrous ethanol (99.5%) supplied by Fisher Scientific. The reaction was
catalyzed by sodium hydroxide pellets supplied by Fisher Scientific. The aqueous phase obtained
from biodiesel reaction was neutralized using 5% sulfuric acid supplied by Fisher Scientific.

2.2 Method for measuring concentration of glycerin

In order to measure the glycerin concentration during the tests, an Abbe 3L Refractometer
AKA Bausch refractometer was used. Using a lab balance (0.1 milligram), several known
concentrations of distilled water and glycerin were prepared. The known solution was used to
generate a calibration curve. This curve correlated the refractive index vs the weight percent of
glycerin in the mixture (w/w%).

To construct the calibration curve, a solution of Glycerin USP (pure) and distillated water in
different concentrations was made. The refractive index was measured for each solution and a graph
was generated which is shown as Figure 1.

1.48
Refractive Index

1.46
1.44
1.42
1.4
y = 0.1375x + 1.3281
1.38 R² = 0.99809
1.36
1.34
1.32
0% 20% 40% 60% 80% 100%

Concentration of glycerin (wt%)

Figure 1 – Calibration curve utilized for measuring glycerin concentration using a refractometer.

2.3 Apparatus
New equipment was developed to perform the experiment. The apparatus was first designed
using Solid Works (2014) Software and built using a 3D printer with ABS plastic. The apparatus
consisted of two parts. One chamber holds silica gel. Crude glycerin was kept in the other
compartment. The parts were connected with plastic tubes through an air compressor. The entire setup
was in a closed loop of air flow. Air after passing through crude glycerin was send to the silica gel
compartment to be dried. The dry air was recirculated to the glycerin compartment by a miniature size
compressor (HARGRAVES). Considering the fact that vapor pressure of water is much higher than
glycerin, air could remove water from crude glycerin. Additionally, unreacted alcohol was carried by
the air and absorbed by the silica gel. Overall, crude glycerin lost water and alcohol. Soluble salts
(after neutralization of crude glycerin with sulfuric acid) were precipitated as fine solids. Removing
water caused over saturation for solution of salt that produced solid salt. Inside of each compartment,

there was a vertical plastic tube that directed air to the bottom of solution and silica gel compartment.
This mechanism provided maximum residence time between solution or silica gel with air.
Consequently, it increased the mass transfer considerably by distributing air at the bottom of each
compartment. Each compartment has a cap to isolate it from atmosphere. The cap is removable for
charging the chemical to the compartment or removing it. The cap has a groove with an O-ring to seal
and make sure the air does not escape. The developed apparatus is shown in Figure 2.

Compressor

Part II Part I

Figure 2 – Apparatus assembly, where part I and II are the solution and silica gel compartments

2.4 Purification of glycerin

The procedure for purification of crude glycerine was primarily tested using USP glycerine to
prove the concept of using silica gel, thereafter, the biodiesel was produced to obtain the crude
glycerine which was used as crude glycerin.

USP Glycerin: The apparatus was prepared to start the purification process. First, a 2-g
sample of silica gel was placed inside part II of the apparatus and 3mL of glycerine-water solution
previously prepared (>45% wt. glycerine) was placed in the other compartment. The process was
executed by several experiments. Each run took 0.5 hours. After 0.5 hour, the glycerine solution was
tested to measure the refractive index and to find concentration of glycerin.

Crude Glycerin: The same procedure was applied to the crude glycerine that was separated
from produced biodiesel as the by-product (glycerine). Thereafter, the glycerin was neutralized with
sulfuric acid (H2SO4 5%) until pH 5-6; the fatty acids were removed by separation funnel. The
remaining solution containing glycerine (>68% wt.), salt, water and very trace amount of soap was
utilized to be purified. During the process it was observed that when glycerin concentration reached a
certain level (about 70 % wt.), salt was precipitated as fine crystals. Fine solids were collected at the
bottom of the apparatus.

3. RESULTS AND DISCUSSION

3.1 Purification of glycerin using silica gel

Figure 3 show that the glycerine-water solution with concentration of about 48% was purified
to concentration of +99%. The overall duration of this experiment was 13 hours (27 steps, each half
an hour). The result is promising considering that other researchers used costly methods to obtain
glycerin +93% (Carmona et al., 2009 and Kongjao et al., 2010).

110
Concentration (wt %)

100
90
80
70
60
50
40
30
20
10
0
1 3 5 7 9 11 13 15 17 19 21 23 25 27

Experiment runs
Figure 3 – Number of steps that required to purify USP glycerin from water solution

The results using the crude glycerin originated from the produced biodiesel are shown in
Figure 4. Regardless the fact that the crude glycerin had more impurities as explained previously, it
took almost the same steps to achieve the desired concentration. It can be concluded that those
impurities do not have observable impact on mass transfer and overal performance of this process.
Nevertheless, it was also possible to achieve a high pure grade of +99% glycerin.

110
Concentration (wt %) 100
90
80
70
60
50
40
30
20
10
0
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Experiment runs
Figure 4 – Crude glycerin concentration during the purification process using designed apparatus

3.2 Regeneration of sorbents

As mentioned before, the sorbent used was silica gel. This material has the capacity to adsorb
water, however, in the developed apparatus the sorbent needs to be regenerated. Regeneration process
could revive the sorption capacity of silica gel. Regeneration was carried out at 100⁰C for half an
hour.

In order to prove that silica gel does not loss its sorption capacity, sorbent was tested
through many cycles of sorption and desorption. The process basically was to introduce a small
mass of the silica gel into a saturated water vapour atmosphere in a closed container until the
sorbent adsorbs maximum possible amount of moisture. The color of silica gel was the best
indicator to determine the end of sorption process. The color of gel went from orange to green.
The weight gains and losses of silica gel were recorded and shown in Figure 5. It is obvious that
even after 50 cycles silica gel does not lose its sorption capacity.

Figure 5 – Initial and final mass of silica gel during sorption/desorption cycles.

4. CONCLUSIONS
The results from this study proved the concept that crude glycerin can be purified at ambient
pressure and temperature. The main goal of this research was not to develop an equipment that
converts the crude glycerin to concentrated form continuously. This method needs more rigorous
study in order to develop optimum equipment that enhances mass transfer between different phases.
However, it was proved that glycerin with different chemical impurities such as salts, water, alcohol
can be purified with no technical issue. The impurity does not have any measurable impact on the
performance of this method. Additionally, glycerin with +99% purity could be obtained easily and
silica gel can be reused many times without losing its sorption capacity. These results are aligned with
the project’s main idea to produce pure glycerin using a simple and low cost method. Further
investigation is required to optimize the design and develop a new equipment and process for
continuous production of glycerin.

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FANG, Y.T.; LIU, T.; ZHANG, Z.C.; GAO, X.N. Silica gel adsorbents doped with Al, Ti, andCo ions
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