Epichlorohydrin

PAMANTASAN NG LUNGSOD NG MAYNILA
University of the City of Manila

College of Engineering and Technology
Department of Chemical Engineering
Dehydrochlorination of
Trihydroxypropane
derived from Crude Glycerol for the
Production of Epichlorohydrin
Submitted by:
DIONISIO, Charles Amiel P.
MENDOZA, Marian D.
RAYMUNDO, Karl Joshua O.
SALIGUE, Mikho Yves M.
YUMUL, Maria Lara Angela B.
BS ChE V
Submitted to:
Engr. Milagros R. Cabangon
Dr. Denvert C. Pangayao
Engr. April Anne Tigue
03 January, 2019
Dehydrochlorination of Trihydroxypropane derived from

Crude Glycerol for the Production of Epichlorohydrin Project Study 1
Dionisio, Mendoza, Raymundo, Saligue, Yumul
PROJECT
STUDY

CHAPTER I
Introductio
n

BACKGROUND OF THE STUDY
Epichlorohydrin (ECH) is a scarce commodity in the Philippines. It

is used largely in the production of epoxy resins, synthetic glycerin,
epichlorohydrin elastomers, specialty water treatment chemicals, wet-
strength resins for paper production, and surfactants. According to the
reports of Philippine Statistics Authority and UN Commodity Trade,
there have been no recorded local production of epichlorohydrin in the
Philippines for the years 2012-2016. Due to the commodity’s local
status, the Philippines must rely on importation to satisfy the local
demand. This importation amounted to 154,487 kg in 2017 which has
a 158% increase since 2012 (Philippine Statistics Authority and UN
Commodity Trade, 2017). This increase reflects the continuous increase
in demand of the commodity in the country.
In order to meet the demand for epichlorohydrin, this commodity
is produced using propylene as a raw material. However, according to
Komiyama (2015), global production of petroleum and its derivatives is
forecasted to decrease by 39.47%. Moreover, according to Ritchie and
Roser (2018), it is estimated that crude oil reserves expected to only
be able to supply the world for only another 50.7 years. The decreasing
supply of crude oil would steeply increase the price of crude oil and its
derivatives, which includes epichlorohydrin.

Moreover, epichlorohydrin can be produced from glycerol through

a two-step process, hydrochlorination and dehydrochlorination (Almena
and Martin, 2016). Additionally, glycerol can be obtained from crude
glycerol through purification wherein crude glycerol undergoes
acidification and vacuum distillation. In line with this according to the
Global Agricultural Information Network, the Philippines produced 350
million liters of biodiesel in 2016, of which the crude glycerol by-
product amounted 30.38 million liters. Moreover, the Biofuels Act or
Republic Act (RA) 9367 that has mandated a minimum one percent
biodiesel blend in all diesel fuels on 2007, which was then raised to 2%
by 2009, then 5% by 2015, projected to 10% increased by 2020, and to
20% by 2030 showed that crude glycerol generation will also increase.
The abundance of crude glycerol and its potential to be a
renewable raw material for epichlorohydrin production has led the
researchers to develop the study “Dehydrochlorination of
Trihydroxypropane derived from Crude Glycerol for the
Production of Epichlorohydrin”.

STATEMENT OF THE PROBLEM
Epichlorohydrin is used in the production of a wide variety of

products, mainly those that require epoxy resin, which gives it a
worldwide production of around 2 million tons per year (Lari, Pastore,
Mondelli, & Pérez-Ramírez, 2018). Due to the variety of its applications,
its demand here in the Philippines has steadily increased with the
highest importation amounting to 154,487 kg recorded in 2017, with
the supply hardly jumping to 6,028 kg from the zeros that were
recorded for years 2012-2016 (Philippine Statistics Authority & U.N
Comtrade). This made the proponents intent to locally produce
epichlorohydrin.
The conventional way of producing epichlorohydrin is a multi-
step process based on propylene, which is obtained petrochemically
(Solvay Chemical Technology, 2016). However, less propylene is being
produced as a co-product due to the increasing use of cost-advantaged
natural gas liquids as a feedstock petrochemical industry (Economic
Plant News, 2015). Another way of producing epichlorohydrin is by
reacting allyl alcohol with chlorine (U.S Patent 4634784). This allyl
alcohol uses pure glycerin as one of its intermediates (LG Chem, Ltd.,
2013) which makes its synthesis complicated and expensive. Due to
this, researchers venture into coming up with a potential abundant raw
material to be used for the less complex production of epichlorohydrin.
Crude glycerol, which contains trihydroxypropane that can be
chemically converted to produce epichlohydrin, can be obtained from
the by-product of biodiesel industry. In general, approximately 1.0 kg of
this co-product is obtained for every 10.0 kg of biodiesel produced
(Chen & Walker, 2011). This glycerol contains many impurities such as

soap and methanol, thus, its conversion and purification into a material
that can be used in the food, cosmetics, or pharmaceutical industries is
prohibitively expensive (Ethier, et. al., 2010). Biodiesel producers, also,
have little incentive in its purification because the price of refined
glycerol has been becoming painfully low (Dobson, et. al., 2011). At
present, most of the crude glycerol is disposed in rivers or simply
incinerated, making biodiesel a grey fuel rather a green fuel (Anand &
Saxena, 2012). And, as more crude glycerol was continuously
generated over the years due to the rapid growth in biodiesel
production, a dramatic decrease in crude glycerol price, hovering
$0.09-0.10/lb, has resulted (ICIS News, 2018). With this, its utilization
in other commercial applications is needed for its surplus problems and
to enhance the economic viability and sustainability of the biodiesel
industry (Dobson, et. al., 2011).
Due to the facts presented, local production of epichlorohydrin
from an abundant renewable source is necessary. Thus, the
researchers proposed the study "Dehydrochlorination of
Trihydroxypropane derived from Crude Glycerol for the
Production of Epichlorohydrin".

OBJECTIVES OF THE STUDY
A. General
The main objective of this study is to design a
manufacturing plant that produces epichlorohydrin from crude
glycerol via catalytic conversion
B. Specific
This study aims to attain the following specific objectives:
 To produce epichlorohydrin that will conform to that of
the properties of the standard and commercial product
presented in Table 1.1.;
Table 1.1 - Standard and Commercial Properties of

Epichlorohydrin
a Commercial
Property Unit Standard c Proposed
Appearance - Clear liquid Clear liquid Clear liquid

pungent, pungent, pungent,
Odor - chloroform- chloroform- chloroform-
like like like
Boiling Point °C 116-118 114-117 114-118
Flash Point °C 31-34 28-33 28-34
Density g/cm3 1.18-1.20 1.18-1.19 1.18-1.20
Viscosity (20
cP 1.03 1.04-1.12 1.03-1.12
°C)
Refractive
1.4358-
Index - 1.4358 1.4358
1.4419
(25 °C)
2,960 (CH2, 2,960 (CH2, 2,960 (CH2,
asymmetric), asymmetric), asymmetric),
Infrared
cm-1 2,906 (CH2, 2,906 (CH2, 2,906 (CH2,
Spectra
symmetric), symmetric), symmetric),
2,867 (C-H) b 2,867 (C-H) b 2,867 (C-H) b
Mass m/z Top peak: 57 Top peak: 57 Top peak: 57
Spetrometry 2nd highest: 2nd highest: 2nd highest:
(Gas 27 27 27
Chromatograph rd
3 highest: rd
3 highest: 29 rd
3 highest:

a a
y) 29 29
a
PUBCHEM Open Chemistry Database,
https://pubchem.ncbi.nlm.nih.gov/compound/epichlorohydrin
b
Shodhganga, FTIR and FTR Spectral Analysis of Epichlorohydrin
c
Material Safety Data Sheet (CDH Fine Chemical, Dow Chemical Company, HML
India, Sigma-Aldrich, Solvay, Sonkamal, Thermo Fisher Scientific)
 To determine the market potential of epichlorohydrin

from crude glycerol through demand and supply
projection, and through coming up with a defined
marketing plan and distinct marketing strategies to
assure its salability;
 To develop a detailed manufacturing process for the
production of
epichlorohydrin from crude glycerol with the
corresponding mass and energy balance, equipment
and specifications, layouts, piping system,
instrumentation and process control, safety, and
wastewater treatment; and
 To assess the economic feasibility of producing
epichlorohydrin in the Philippines by determining its
marketability through projecting the future expenses of
the company (including the cost of the raw materials,
equipment, construction and installation, work force,
etc.), the selling price of the product and the return of
investment.

SIGNIFICANCE OF THE STUDY
This study “Catalytic Dehydrochlorination of

Trihydroxypropane from Crude Glycerol for the Production of
Epichlorohydrin” offers various importances to the following
segments of the society:
 To Students and Researchers
This study will provide relative information to those who
are interested in utilizing another renewable raw material for the
production of epichlorohydrin, or are into using crude glycerol to
come up with a different value-added product. Moreover,
students and researchers will be able to apply their knowledge
about the theories and principles presented in this paper which
may lead to developing a safer, more economical process in
producing epichlorohydrin.
 To the Biodiesel Industry

The utilization of crude glycerol will generate an added

income to the growing biodiesel industry and can also be an
additional solution to its increasing waste generation. This will be
of great help in the further growth of the biodiesel industry due
to the Philippines’ Biofuels Act’s 20% blend requirement in 2030.
 To Epichlorohydrin-utilizing Industries
Majority of epichlorohydrin in the Philippines are being
imported for industrial applications. This study will provide a
locally-produced epichlorohydrin which will, of course, cost less
than its imported counterparts and epichlorohydrin-utilizing
industries will benefit from this by getting to have a lower capital
for their raw material.

SCOPE AND LIMITATION

Scope
The study aimed to produce epichlorohydrin from crude glycerol

through purification, hydrochlorination and dehydrochlorination. It
covers the market study of the product, laboratory and industrial
design of the process, and the different unit operations and processes
involved in the production of epichlorohydrin from crude glycerol. The
industrial-scale materials and energy balances, unit operations and
processes involved are taken into consideration in the design of
different appropriate equipment to produce the epichlorohydrin, which
conforms to the standard product properties. The data and
assumptions based from the experiment are also considered in the
design calculations for each equipment. The piping system of process,
hot water, chilled water and steam, as well as the instrumentation and
process control are also indicated.
The raw material properties were gathered from Chemrez

Technologies Inc., while its statistics were obtained from the Philippine
Coconut Authority. Furthermore, the data of the product was obtained
from Philippine Statistics Authority and UN Commodity Trade.
For the experimental study, the crude glycerol is obtained from

Chemrez Technologies Inc. The reagents and apparatus were
purchased from Alysons’ Chemical Enterprises and RB Chemodities
Marketing. The experiment was performed at PLDTSFH-CHE-LAB.
The optimum parameters were determined during the

experimental study. Then, analyses of the demand and supply of the
product were performed, data was collected from 2012 to 2017 and

the value for the succeeding years up to 2024 was determined using
different projection methods for the marketability. Lastly, the design of
different equipment for unit operations and processes involved in the
study were dependent on the results of the experimental study.
Limitation
Some online resources such as journals and related studies were

limited to the abstract part only as it requires expensive subscription to
have complete access on the whole document. For the raw material,
crude glycerol is only obtained from Chemrez Technologies Inc., while
the other possible raw material sources were not tested for their crude
glycerol composition. Lastly, experimental procedure is done on a
laboratory scale only and errors as well as deviations in the study are
expected.

CHAPTER
II
Review of
Related

Literature and
Studies

REVIEW OF RELATED LITERATURE
A. PRODUCT
Epichlorohydrin
Epichlorohydrin is a colorless liquid with a
pungent, garlic-like odor, moderately soluble in
water, but miscible with most polar organic
solvents. It is an organochlorine compound and
an epoxide. It is a highly reactive electrophilic
compound and is used in the production of
epoxy resins, adhesives, elastomers, plastics, Figure 1.1 -
Epichlorohydrin
rubbers, and paper, which gives it a worldwide
scale of around 2 million tons per year (Lari, Pastore, Mondelli, & Pérez-
Ramírez, 2018). It is used as a major component in its applications
except paper production wherein it is used as a strength additive
(Bower, 2000).
In its main application as epoxy resins, it is used in protective

coatings including those used for lining food and beverage containers
(Solvay, 2007). They are also used in structural applications such as
circuit board laminates, semiconductor encapsulants, and structural
composites; tooling, molding and casting; flooring, adhesives, paints
and other coatings.
Epichlorohydrin consists of three carbon chain, with a chloride

attached to one end and an epoxide ring at the other end (as seen in
Figure 1.2).

Figure 1.2- Structure of Epichlorohydrin
Product Properties
Epichlorohydrin, a liquid product, follows a set of standard and

commercial properties that are set to suit its applications in the
industry. The chemical properties of standard and commercial
epichlorohydrin is summarized in Table 1.2 together with the
properties of the proposed product. Moreover, the product can be
characterized by using infrared spectrometry or gas chromatography,
which ensures its safety, purity and identity.
Table 1.2 - Standard and Commercial Properties of

Epichlorohydrin
Property Unit Standard a Commerci Proposed
al c
Color - Colorless Colorless Colorless

Boiling Point °C 116-118 115-117 115-117
Flash Point °C 31-34 32 32-33
Solubility - soluble in 65.9 g/L in 55-60 g/L in
water (50- water at water
mg/mL at 25°C
20-25 °C);
miscible
with most
organic
solvents
Density g/cm 3
1.18-1.20 1.183 1.18-1.20
Viscosity Poise 0.0103 at 0.012 0.01-0.012

25 °C
Infrared Spectra cm -1
2,960 (CH2, - 2,960 (CH2,
asymmetric) asymmetric)
, 2,906 (CH2, , 2,906 (CH2,
symmetric), symmetric),
2,867 (C-H) 2,867 (C-H)
b b
Mass m/z Top peak: - Top peak: 57

Spectrometry 57 2nd highest:
(Gas 2nd highest: 27
Chromatography 27 3 highest:
rd
) 3rd highest: 29
29
a
PUBCHEM Open Chemistry Database,
https://pubchem.ncbi.nlm.nih.gov/compound/epichlorohydrin
b
Shodhganga, FTIR and FTR Spectral Analysis of Epichlorohydrin
c
Sigma-Aldrich Epichlorohydrin MSDS,
https://www.sigmaaldrich.com/catalog/product/sial/ 02578?
lang=en&region=PH&cm_sp=Insite-_-prodRecCold_xviews-_-prodRecCold5-4
Due to the increase in the applications of epichlorohydrin, the

demand for epichlorohydrin in the Philippines has steadily increased as
reflected in the data reported by Philippine Statistics Authority
(summarized in Table 1.3). The increasing amount of importation of
epichlorohydrin shows that, in order to meet the demand of
epichlorohydrin in the Philippines, the country needs to rely solely in
importation. The highest importation was recorded on 2017 amounting
to 154,487.00 kg, while the highest exportation (6,028.00 kg) was
recorded in the same year.
Table 1.3 - Philippine Epichlorohydrin Importation and

Exportation (2012-2017)
Year Importation (kg) Exportation (kg)
2012 59,836 0
2013 91,552 0

2014 60,044 0
2015 85,955 0
2016 79,069 0
2017 154,487 6,028
Figure 1.3 - Philippine Epichlorohydrin Importation and

Exportation (2012-2017)
The data presented in Figure 1.3 shows that there is a
significant increase in the amount of importation of epichlorohydrin
between 2016 and 2017, having a growth rate of 95.38%. On the other
hand, there were no documented exports of epichlorohydrin in the
Philippines from 2012 to 2016, until an increase in supply, amounting
to 6,028 kg, was reported in 2017.
The current epichlorohydrin market trend indicates that the
supply of epichlorohydrin is not expected to meet the demand in future
years and will continue to rely on importation. Thus, higher production
of epichlorohydrin in the Philippines is needed in order to meet the
increasing epichlorohydrin demand.

B. PROCESS
Currently, epichlorohydrin is produced through a three-step
process using propylene as the major raw material. The first process is
the chlorination of propylene to form allyl chloride. Then, allyl chloride
is reacted with hypochlorous acid to produce dichlorohyrin. Finally, the
produced dichlorohydrin is subjected to dehydrochlorination reaction to
produce epichlorohydrin and by-products water and salt. The reaction
series is shown in Figure 1.4 below.
Figure 1.4 – Propylene to Epichlorohydrin Reaction Mechanism
However, according to Komiyama (2015), global production of

petroleum and its derivatives is forecasted to decrease by 39.47%.
Moreover, according to Ritchie and Roser (2018), it is estimated that
crude oil reserves expected to only be able to supply the world for only
another 50.7 years. The decreasing supply of crude oil would steeply
increase the price of crude oil and its derivatives, which includes
epichlorohydrin.

Considering the current status of propylene and the increasing

demand for epichlorohydrin, the proponents have come up with a
process which converts crude glycerol to epichlorohydrin through
glycerol purification, hydrochlorination, and dehydrochlorination as
shown in Figure 1.5.
Figure 1.5 – Glycerol to Epichlorohydrin Reaction Mechanism
Crude glycerol is first purified through acidification process, which is

done to reduce the free fatty acid content of the crude glycerol. The
crude glycerol will be reacted with an acid and settled until it separates
into two distinct layers, a top layer of free fatty acids and the bottom
glycerol layer. The top layer is removed by decantation, and the
remaining glycerol is used as feedstock for the next process.
Figure 1.6 – Hydrochlorination of Glycerol using Hydrogen

Chloride
The purified glycerol will then be converted into dichlorohydrin
(DCH) via hydrochlorination, which is an addition reaction in which

hydrogen chloride is added to a compound. The hydrochlorination of

glycerol to dichlorohydrin (DCH) reaction mechanism is shown in
Figure 1.6 above, where one mole of glycerol is reacted with two
moles of aqueous hydrogen chloride (HCl) to produce one mole of DCH.
In order to speed up the reaction rate and conversion of hydrogen
chloride with glycerol, a catalyst is used.
Typically, a carboxylic acid, such as acetic acid, is used as the

catalyst for hydrochlorination because it has the ability to stop the
reaction when DCH is formed instead of reacting to trichloropropane
(TCP) (Bell et al., 2008). Formation of TCP would result in a less efficient
process with less DCH obtained from glycerol and an extra separation
step to purify the DCH.
Figure 1.7 – Dehydrochlorination of DCH
Afterwards, DCH is converted to the final product via

dehydrochlorination. In contrast to the previous process,
dehydrochlorination is the removal of hydrogen chloride from a
compound. In the conversion of dichlorohydrin to epichlorohydrin, a
base reactant such as sodium hydroxide is used. As shown in Figure
1.7, hydrogen chloride will be removed from the structure of
dichlorohydrin and reacted with the base reactant to form the by-
products salt and water, while the dichlorohydrin will form 1-Chloro-
2,3-epoxypropane which is commonly known as epichlorohydrin
(Almena & Martin, 2016).

The following processes after dehydrochlorination reaction:

filtration, solvent extraction, and distillation, are mainly for product
purification. Filtration is done to remove the salt precipitate from the
mixture. However, the remaining water and epichlorohydrin mixture
cannot be separated through simple or fractional distillation as it forms
an azeotrope having a composition of 26 wt% water and 74 wt%
epichlorohydrin, and an azeotropic boiling point of 88 C. Thus,
O
epichlorohydrin will be extracted from the mixture via solvent

extraction.
Solvent extraction is a method to separate compounds based on

their relative solubilities in two different immiscible liquids, where the
solvent used is usually an organic compound. In choosing the suitable
solvent to be used in this process, the substance should be non-polar
and has a high selectivity towards ECH (S. P. Jeevan Kumar, 2017). The
resulting ECH-solvent mixture will be subjected to distillation process
to extract the final product which is epichlorohydrin.
C. RAW MATERIAL
In the proposed process above, the major raw

material is crude glycerol (shown in Figure 1.8),
which is a by-product in the biodiesel manufacturing
process. According to Teng et al. (2014),
approximately 10% of the produced biodiesel could
Figure 1.8 –
be collected as crude glycerol. As the conventional
Crude
biodiesel plants mostly utilize base-catalyzed Glycerol
transesterification method, the obtained crude glycerol has an average

purity of 75% containing traces of methanol, salt, catalyst residue,

soap, fatty acids and glycerides (Gonzalez et al., 2005).
Figure 1.9 – Glycerol as a By-product of Biodiesel Production
In the Philippines, biodiesel production capacity has been well

developed in recent years due to the Biofuels Act of 2007. The Biofuels
Act or Republic Act (RA) 9367 mandated a minimum 1% biodiesel blend
in all diesel fuels by February 2007, and to increase to a 2% blend after
2 years, and raise to 5% by 2015, 10% by 2020, and to 20% by 2030
(Corpuz, 2015). With this increase in demand in biodiesel, it is
expected that there would also be a significant increase in its
production, thereby increasing crude glycerol generation as a result.
According to Philippine Department of Energy (DOE), as of now,

there are eleven (11) registered and operational biodiesel refineries,
with an aggregate annual capacity of 585 Million Liters (MLi). Total
capacity increased 48% from 393 MLi in 2013 to 585 MLi in 2014.
Additionally, the average annual production of biodiesel was 172
Million Liters (MLi) in 2014 and was increased to 190 MLi on 2015.
Based on DOE data, except for 2010, biodiesel production has been
increasing and continued to surge to 350 MLi by 2016. Table 1.4

below shows the biodiesel production in the Philippines on a daily

basis.
Table 1.4 – Biodiesel Production in the Philippines from 2004 –

2016
VALUE (in thousand

YEAR
barrels/day)
2004 0.00
2005 0.00
2006 0.00
2007 0.80
2008 1.10
2009 2.40
2010 2.10
2011 2.30
2012 2.40
2013 2.70
2014 3.00
2015 3.50
2016 3.90
Source: Philippines Biodiesel Production, World Data Atlas
Since approximately 10% of the biodiesel production accounts for

the crude glycerol, the crude glycerol production in the Philippines is
calculated and summarized in Table 1.5 below.
Table 1.5 – Crude Glycerol Production in the Philippines from
2004 – 2016
VALUE (in thousand

YEAR
barrels/day)
2004 0.00
2005 0.00
2006 0.00
2007 0.08

2008 0.11
2009 0.24
2010 0.21
2011 0.23
2012 0.24
2013 0.27
2014 0.3
2015 0.35
2016 0.39
Source: Philippines - Biodiesel Production, World Data Atlas
Table 1.6 presents the major biodiesel manufacturing plants in the
Philippines in 2011, and their corresponding capacity. The companies
listed below are the possible sources of crude glycerol as raw material
for the production of epichlorohydrin.
Table 1.6 - Major Biodiesel Manufacturing Plant in the

Philippines as of 2011
Source: Philippine Coconut Authority
A sample of local crude glycerol, obtained from Chemrez

Technologies Inc. located in Bagumbayan, Quezon City, was found to
have the following composition (shown in Table 1.7 below) which can
be converted to value-added products such as epichlorohydrin.

Table 1.7 – Composition of Crude Glycerol

Properties Test Method Results Specifications
Clear light
Occular Clear light
Appearance brownish
Inspection brownish liquid
liquid
Karl Fischer
Water Content, % 8.56 15 max.
Method
Glycerine Assay, % AOCS Ea 6-94 64.15 60 min.
Fatty Acid &
USP 20th Ed 24.48 28 max.
Esters, %
Ash Content, % ASTM D 874-82 2.64 8 max.
Methanol Content,
USP 20th Ed 0.034 1 max.
%
MONG, % In-house 0.66 3 max.
pH pH Meter 6.56 5-8
Source: Chemrez Technologies Inc., 2018
Currently, a large portion of crude glycerol goes into animal

feedstock as cattles can tolerate poisonous methanol-contaminated
raw glycerol, and still efficiently absorb the energy content of the
molecule. It has also been proven that by adding 7.5 wt% crude
glycerol to cattle rations, the animal’s feed to weight-gain ratio
improves. In addition to this, the only other major use of crude glycerol
is as an additive for manufacturing cement of enhanced performance
(enhanced concrete strength, grinding, and handling aid for cement)
replacing petrochemical amines and glycols [ CITATION Pag14 \l 1033 ].
Aside from these, crude glycerol has no other major use and is
treated as a waste product of biodiesel companies. Various methods for
disposal and utilization of this crude glycerol have been attempted,
including combustion, composting, and anaerobic digestion. However,
these methods are not economical for large-scale disposal of crude
glycerol (Yang et al., 2012).

To be utilized commercially in other industries, crude glycerol must

first be further purified to technical grade glycerol or USP grade
glycerol of which the specifications are listed in Table 1.8 below.
Table 1.8 – Classification of Glycerol and its Specifications
Technical
USP Grade
Properties Crude Glycerol Grade
Glycerol
Glycerol
Glycerol Content 40 – 88% 97.0 Min 99.70%
Ash 2.0% Max N/A N/A
Moisture Content N/A 2.0% Max 0.3% Max
Chlorides N/A 10 ppm Max 10 ppm Max
10 Max.
Color N/A 40 Max (Pt – Co)
(APHA)
Specific Gravity N/A 1.262 (@25C) 1.2612 Min
Source: SRS International Biodiesel, 2018
Crude Glycerin – Crude glycerin contains a significant amount of
methanol, water, soaps, and salts and typically has a glycerol content
of anywhere between 40 to 88%. Crude glycerol is a natural by-
product produced during the biodiesel production process, specifically
taking place during transesterification.
Technical Grade Glycerin – Technical grade glycerin is a refined
product with most of its contaminants removed. Technical grade
glycerin contains no methanol, soaps, salts, and other foreign matter.
This is typically used in industries that doesn’t involve products
designed for human consumption such as alkyd resins and paper
products.
USP Grade Glycerin – USP Grade Glycerin is a pharmaceutical
grade, high-purity glycerin suitable for food, personal care, cosmetics,
pharmaceuticals, and other specialty applications that have met the
US Pharmacopeia specifications (USP 30).

The main property that classifies glycerol into different types is its
purity or glycerol content, and generally, the higher the purity, the
more processes are involved and the higher the cost of production.
The largest local consumers of glycerol (shown in Figure 1.10

below), which are the cosmetics, food and pharmaceutical industries,
require high-purity USP grade glycerol which is expensive to produce
via crude glycerol refining as it requires additional processes compared
to technical grade glycerol [ CITATION Sal10 \l 1033 ]. Due to this,
crude glycerol is barely utilized and is treated as a waste product.
Philippine Glycerol Consumption

Cosmetics, Soaps,
Pharmaceuticals
Alkyd Resins
12.00%
26.00% Food and Drink
17.00% Tobacco
Cellulose Films
1.00% 6.00%
11.00% Polyglycerol Esters
4.00%
3.00% Esters
8.00% Paper
Resale
12.00%
Other Uses
Figure 1.10 – Distribution of Glycerol Consumption in the

Philippines
For large scale biodiesel producers, crude glycerol can be refined

into technical or USP grade glycerol then sold to other industries. For
small scale producers, however, purification is too expensive to be
performed in their manufacturing sites. Their crude glycerol is usually

sold to large refineries or disposed through various methods (Yang et

al., 2012).
However, with the rapid expansion of biodiesel industry, the market

is flooded with excessive crude glycerol. As a result, crude glycerol
prices have dropped significantly, and biodiesel producers receive a
much lesser amount of profit from the sale of crude glycerol compared
to previous years (Taconi, 2017). Thus, crude glycerol is generally
treated as a waste product within the biodiesel industry. In the
Philippines, an excess amount of 17 million kilograms of crude glycerol
was exported from the country in the year 2015 (Philippine Statistics
Authority). With the surplus of crude glycerol and the drop in its
market value, it can be concluded that there is an abundant amount of
crude glycerol that may be utilized as raw material for the production
of epichlorohydrin.

REVIEW OF RELATED STUDIES

Crude glycerol contains 84.14% glycerol (Chemrez Technologies
Inc.) which can be converted to epichlorohydrin through
hydrochlorination and dehydrochlorination. However, in order to utilize
the crude glycerol, it is first purified to technical grade glycerol via
acidification.
Acidification is done to reduce the free fatty acid and salt content of
the crude glycerol. Crude glycerol acidification can be performed by
using sulfuric, hydrochloric or phosphoric acid (Aroua et al., 2015). In
the study conducted by Ooi et al. (2001), crude glycerol was purified
from 34 wt% to 52 wt% via acidification using sulfuric acid. On the
other hand, Tianfeng et al. (2013) proposed acidification of crude
glycerol obtained from waste cooking oil biodiesel production using
5.85% H3PO4 and found an increase in volume of glycerol-rich layer
content from 40% to 70%. As for the time and temperature of the
acidification process, an optimum temperature of 70 OC and reaction
time of 60 minutes was obtained by Hajek et al. (2010) in their study
entitled “Treatment of Glycerol Phase Formed by Biodiesel Production”.
Using these studies as basis, the proponents will use sulfuric,
hydrochloric or phosphoric acid, a temperature range of 60 OC to 90 OC,
and a reaction time ranging from 30 minutes to 90 minutes.
After acidification, the glycerol will be subjected to hydrochlorination

with hydrochloric acid. In this process, the reactant HCl cannot be
varied because it is a specific type of reaction that incorporates
hydrogen chloride into glycerol to form dichlorohydrin (DCH). However,
this process makes use of carboxylic acid catalysts that are less
volatile than the DCH, and any carboxylic acid catalyst with at least six

carbon atoms has a higher boiling point than DCH, hence being less
volatile (Bell et al., 2008). The two carboxylic acids that fit this
description best are acetic acid and malonic acid. For the other
parameters, the study of Hook et al. (2008) obtained an optimum
temperature of 120 O
C, a reaction time of 2 hours, and a catalyst
loading of 8 wt%. Thus, the proponents will vary the catalyst by using
acetic and hexanoic acid, reaction temperature range of 110-140 OC,
reaction time ranging between 60-180 minutes, and catalyst loading of
1% to 5%.
Finally, the intermediate product DCH will now undergo

dehydrochlorination using a liquid base like sodium hydroxide, or solid
alkali oxides such as magnesium oxide and magnesium-aluminum
(Almena & Martin, 2016). In the study of Heeres, A. (2018), DCH was
successfully converted to epichlorohydrin using magnesium-aluminum
as the base, with a reaction temperature of 90 OC and a 120-minute
reaction time. For the optimization of parameters, the proponents will
vary the alkali reactants by using NaOH, MgO, and Mg-Al, temperature
range of 60-120 OC, and reaction time between 60-180 minutes.

Table 1.9 – Summary of Review of Related Studies
Author, Relevant
Process Title
Year Information
Crude glycerol
Progress, prospect
acidification can be
and challenges in
Aroua et done by using
glycerol
al. (2015) sulfuric,
purification
hydrochloric or
process
phosphoric acid.
Characterization of Crude glycerol was
glycerol residue upgraded from
Ooi et al. generated from a purity of 34 wt% to
(2001) palm kernel oil 52 wt% by using
methyl sulphuric acid.
ester plant
Acidification Purification of
Crude Glycerol Using 5.85% H3PO4
from waste resulted to an
Tianfeng
cooking oil based increase in volume
et al.
biodiesel of glycerol-rich layer
(2013)
production by content from 40%
orthogonal test to 70%.
method
Optimum
Treatment of
temperature of
Glycerol Phase
Hajek et 70OC and reaction
Formed by
al. (2010) time of 60 minutes
Biodiesel
was obtained using
Production
phosphoric acid.
Hydrochlorin Bell et al., Glycerin as a Carboxylic acids
ation (2008) Renewable that are less volatile
Feedstock for than the DCH with
Epichlorohydrin at least six carbon
Production. The atoms can be used
GTE Process as catalysts, such
as acetic and
malonic acid.

In
hydrochlorination,
the optimum
Crude Glycerol to parameters are:
Hook et al.
Epichlorohydrin temperature of 120
(2008)
Production O
C, reaction time of
2 hours, and
catalyst loading of 8
wt%.
An alkali compound
like sodium
Technoeconomic
hydroxide, or solid
analysis of the
Almena & alkali oxides such as
production of
Martin magnesium oxide
epichlorohydrin
(2016) and magnesium-
from
aluminum can be
glycerol
used as base
reactants.
DCH was
successfully
converted to
A Novel Method for epichlorohydrin
Dehydro- Refining Crude using magnesium-
chlorination Heeres, A. Glycerol a aluminum as the
(2018) Byproduct base, with a
from Biodiesel reaction
Industries temperature of 90
O
C and a reaction
time of 120
minutes.
Epichlorohydrin and
water cannot be
Herliati et Synthesis of separated via
al. Epichlorohydrin fractional distillation
(2014) from Glycerol because it forms a
26% water and 74%
ECH azeotrope.

REFERENCES
Almena, A., & Martin, M. (2016). Technoeconomic analysis of the

production of epichlorohydrin from glycerol. Industrial & Engineering
Chemistry Research, 55, 3226-3238.
Bell, B. M., Briggs, J. R., Campbell, R. M., Chambers, S. M.,

Gaarenstroom, P. D., Hippler, J. G., et al. (2008). Glycerin as a
renewable feedstock for epichlorohydrin production. the GTE process.
CLEAN – Soil, Air, Water, 36(8), 657-661.
Bower, B. K. (2000). Polyamidoamine/epichlorohydrin resins bearing

polyol sidechains as dry strength agents. Washington, DC: U.S.: U.S.
Patent No. 6,165,322.
Giri, A. K. (1997). Genetic toxicology of epichlorohydrin: A review

doi:https://doi.org/10.1016/S1383-5742(96)00042-7
Ilham, Z. & Saka, S. (2016). Esterification of glycerol from biodiesel

production to glycerol carbonate in non-catalytic supercritical dimethyl
carbonate. DOI: 10.1186/s40064-016-2643-1
Kosmider, A., Leja, K., & Czaczyk, K., (2012). Improved Utilization of
Crude Glycerol
By-Product from Biodiesel Production. Poznań University of Life
Sciences, Poland.
Lari, G. M., Pastore, G., Haus, M., Ding, Y., Papadokonstantakis, S.,
Mondelli, C., et al. (2018). Environmental and economical perspectives
of a glycerol biorefinery. Energy & Environmental Science,
Tan, H. W., Abdul Aziz, A. R., & Aroua, M. K. (2013). Glycerol production
and its applications as a raw material: A review
doi:https://doi.org/10.1016/j.rser.2013.06.035
Wang, M., Zhou, J., Mao, G., & Zheng, X. (2012). Synthesis of TS-1 from
an inorganic reactant system andits catalytic properties for allyl
chloride epoxidation. Industrial & Engineering Chemistry
Research,51(39), 12730-12738.

Wang, S., Wong, D. S., Jang, S., & Huang, S. (2017). Novel plant-wide
process design for producingdichlorohydrin by glycerol
hydrochlorination doi:https://doi.org/10.1016/j.jtice.2016.05.055


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PAMANTASAN NG LUNGSOD NG MAYNILA

University of the City of Manila

Dehydrochlorination of Trihydroxypropane derived from

Dehydrochlorination of Trihydroxypropane derived from

Dehydrochlorination of Trihydroxypropane derived from

BACKGROUND OF THE STUDY