Reformado Glicerine

31/1/2020 Glycerol - an overview | ScienceDirect Topics
Glycerol
Glycerine is an excellent softener as it possesses the desired
softening qualities and is hydroscopic in nature, thus maintaining a
high regain in the yarn.
From: Woven Textiles, 2012
Related terms:
Biodiesel, Transesterification, Hydrogen, Viscosity, Feedstocks, Glycerols,

Phthalates, Resin, Plasticizer
Pyrolysis of Alcohols and Phenols

Serban C. Moldoveanu, in Pyrolysis of Organic Molecules (Second Edition), 2019
Glycerin
Glycerin (glycerol or propane-1,2,3-triol) is a compound widespread in nature
either in free form or, more frequently, as an ester (glycerides). Glycerin can be
considered a sugar alcohol formed by hydrogenation from glycerin aldehyde (a C3
monosaccharide). Large quantities of glycerin are synthesized from epichlorhydrin
and are generated as a byproduct in soap making and biodiesel production.
Glycerin is used as a humectant in the food, beverage, and tobacco industries as
well as a solvent, a sweetener, and a thickening agent.
At temperatures below 350°C, particularly in the presence of silica, metals, and
certain salts such as MgSO4 and K2HPO4, glycerin forms small amounts of
acrolein. Formation of acrolein from the pyrolysis of glycerin is of particular
concern because glycerin is added as a humectant on cigarettes [40]. At
temperatures around 450°C, acetaldehyde and allyl alcohol are also formed. At
even higher temperatures (650°C), glycerin vapors in the presence of water vapors
show, even at short residence time (0.1 s), about 15% decomposition with the
formation of acrolein, acetaldehyde, and formaldehyde as the main reaction
products (in addition to water). The decomposition percent increases considerably
at 750°C, where the glycerin decomposition is almost complete. At this
temperature, other compounds also are present in the pyrolyzate as a result of
subsequent decomposition of acrolein and acetaldehyde as well as of different
paths of direct glycerin decomposition [41,42]. Among the secondary pyrolysis
products are CO, H2, CH4, and C2H4. Traces of CO2, C2H6, C3H6, 1,3-butadiene,
and isobutene also were detected in the pyrolyzate. Fig. 4.1.11 shows the variation
of pyrolysis products of glycerin (diluted to about 1% with steam) in moles per 100
moles converted glycerin at different temperatures. The residence times in the
pyrolyzer were 0.13 s for 650°C and 675°C and 0.048 s for 700°C [36].
https://www.sciencedirect.com/topics/engineering/glycerol 1/16
Fig. 4.1.11. Variation of pyrolysis products of glycerin (diluted with steam) in moles
per 100 moles converted glycerin at different temperatures and a residence time of
0.13 s for 650°C and 675°C and of 0.048 s for 700°C [41].
At the low temperature of 350°C, a pyrogram for 2 mg of glycerin is shown in Fig.
4.1.12. Peak identification is shown in Table 4.1.11. Water was initially present in
glycerin and it is not clear if the other peaks besides glycerin represent in part
impurities in the initial glycerin. Also, in mole % the level of water is very high.
Fig. 4.1.12. Pyrogram of glycerin at 350°C (a wide water peak is seen at 6.39 min).
Peak assignment is given in Table 4.1.11.
Table 4.1.11. Identification of the Main Peaks in the Chromatogram Shown in

Fig. 4.1.12 for the Pyrolysis of Glycerin at 350°C
Retention Moles %
No. Compound Time (Min) MW CAS# Pyrolyzate
1 Air 4.06
2 Water 5.20–7.05 18 7732- 75.77

18-5
Retention Moles %
3 1-Hydroxy-2-propanone 22.19 74 116- 0.36

09-6
4 2-Butoxyethanol 31.10 118 111- 0.38

76-2
5 Glycerin 41.02 92 56-81- 23.25

5
6 2,2,-Dimethyl-1,3-dioxolane-4- 44.13 132 14347- 0.11

methanol 78-5
7 2,2,-Dimethyl-1,3-dioxolane-4- 44.49 132 - 0.13

methanol isomer
Pyrolysis of 2 mg of glycerin at higher temperature of 850°C generates the

pyrogram from Fig. 4.1.13. The other parameters of the pyrolysis were
β = 10°C/ms, THt = 10 s, and housing temperature Thou = 280°C. The analysis of
the pyrolyzate was done by GC/MS under conditions given in Table 1.4.1. Peak
identification is shown in Table 4.1.12.
Fig. 4.1.13. Pyrogram of glycerin at 850°C. Peak assignment is given in Table

4.1.12.
Table 4.1.12. Identification of the Main Peaks in the Chromatogram Shown in

Fig. 4.1.13 for the Pyrolysis of Glycerin at 850°C
Retention Moles %
1 Air 4.22 – –
2 Formaldehyde 4.50 30 50-00- 4.93

0
3 Water 5.30 18 – 5.29
Retention Moles %
4 Acetaldehyde 5.66 44 75-07- 7.09

0
5 2-Propenal (acrolein) 8.35 56 107- 9.47

02-8
6 2-Oxopropanal (glyoxal) 9.15 72 78-98- 0.18

8
7 2-Propen-1-ol 12.93 58 107- 2.08

18-6
8 Hydroxyacetaldehyde 17.25 60 141- 0.63

46-8
9 2-Ethoxypropane 19.27 88 625- 0.40

54-7
10 Acetic acid 19.99 60 64-19- 0.22

7
11 1-Hydroxy-2-propanone 22.20 94 116- 4.63

09-6
12 Acetoin 24.04 88 513- 0.07

86-0
13 Propanoic acid 25.01 74 79-09- 0.04

4
14 Glycidol 25.56 74 556- 2.75

52-5
15 Propylene glycol 27.98 76 57-55- 0.26

6
16 Unknown 30.62 74 – 0.05
17 2-Methyl-4-methylol-1,3- 32.65 118 – 0.11

dioxolane
18 4-Methanol-1,3-dioxolane 32.93 104 86687- 0.07

05-0
19 5-Methyl-3,6,8- 33.22 130 30120- 0.03

trioxabicyclo[3.2.1]octane 60-6
20 trans-4-Hydroxymethyl-2- 33.78 118 – 0.06

methyl-1,3-dioxolane
21 2-Vinyl-1,3-dioxolane-4- 36.98 130 4313- 0.06

methanol 32-0
22 2-Vinyl-1,3-dioxolane-4- 37.71 130 – 0.05

methanol (isomer)
23 Glycerin 42.40 92 56-81- 60.92

5
24 2,2,-Dimethyl-1,3-dioxolane-4- 44.13 132 14347- 0.29

methanol 78-5
Retention Moles %
25 2,2,-Dimethyl-1,3-dioxolane-4- 44.58 132 – 0.32

methanol isomer
Note: Bold numbers indicate large component in the pyrolyzate.
The pyrolysis mechanism of glycerin pyrolysis very likely consists of both radical
initiated reactions and nonradical initiated reactions. The formation of acrolein
would be expected to occur as the result of the following sequence:
(4.1.33)
However, free radical inhibitors such as NO affect the formation of acrolein. For
this reason, a mechanism involving free radicals is considered as dominant in the
acrolein formation, shown as follows:
(4.1.34)
The decomposition following reaction (4.1.34) to the step of an aldol formation can
continue with a retro-aldol reaction, as shown below [42]:
(4.1.35)
Acetaldehyde also can be generated directly from glycerin by radical reactions, as

shown below:
(4.1.36)
However, both reactions (4.1.35) and (4.1.36) predict the formation of equal
quantities of formaldehyde and acetaldehyde, which is not in agreement with the
experimental data. Possibly some formaldehyde is decomposed into H2 and CO, or
other fragments are generated as a side result of reaction (4.1.34).
The study of the kinetics of glycerin decomposition [41] indicated that the reaction
can be considered unimolecular and follows the Arrhenius equation:
(4.1.37)
One potential application of glycerin pyrolysis is the production of combustible gas

mixtures. Because glycerin is a byproduct of several industrial processes
particularly related to biodiesel, an excess of glycerin would be available on the
market if biodiesel production increased. For this reason, glycerin utilization for the
generation of gaseous fuels such as H2, synthesis gas (syn gas), or CH3OH is of
considerable interest. Because pyrolysis of glycerin at elevated temperatures
(around 800°C) produces mainly a mixture of CO, H2, CO2, CH4, and C2H4 (similar
to that of synthesis gas), various studies were geared toward the optimization of
this process [43,44].
HEALTH, SAFETY AND ENVIRONMENTAL ISSUES

In Handbook of Antiblocking, Release, and Slip Additives (Third Edition), 2014
16.2.4 OTHER CHEMICAL COMPOUNDS

Glycerin. Adverse effects following oral administration of glycerin include mild
headache, dizziness, nausea, vomiting, thirst, and diarrhea. Glycerin poses low risk
health effects from vapors that can be regarded as a nuisance rather than toxic.
Repeated application of 100% glycerin to the surface of the eye causes extensive
changes in the appearance of the endothelium, but most of these changes
disappear within 90 min after exposure is ended. OSHA PEL is 15 mg/m3 (mist,
total dust) and 5 mg/m3 (mist, respirable fraction). ACGIH TWA is 10 mg/m3 and
30 min maximum concentration of 50 mg/m3. If released to water, glycerin is
expected to rapidly degrade under aerobic conditions. Biodegradation in seawater
and under anaerobic conditions is also expected. Glycerin is not expected to
bioconcentrate in fish and aquatic organisms, nor is it expected to adsorb to
sediment and suspended organic matter.
Stearyl alcohol. Higher alcohols are not considered toxic. If released to soil, stearyl
alcohol is not expected to be mobile, due to strong soil adsorption. Biodegradation
may be an important process in soil. If released to water, it will adsorb to
suspended solids and sediment.
Glycerol monostearate. There is no human or animal information available
regarding toxicity, carcinogenicity, and mutagenicity. Glyceryl monostearate is
probably non-toxic. High concentrations of dust may cause coughing and mild,
temporary irritation. A number of human studies have been conducted, both on
normal subjects and patients with eczema. In each case, glycerol monostearate was
found to be essentially non-irritating or mildly irritating.
Pentaerythritol tetrastearate. The toxicological properties of this material have not
been fully investigated. The substance is not registered with any testing agency and
no animal studies were reported.
Dioctyl sodium sulfosuccinate. Considered moderately toxic. Probable oral lethal
dose for humans is 0.5–5 g/kg. If released to soil, the expected mobility of dioctyl
sodium sulfosuccinate is from low to very high. If released to water, dioctyl sodium
sulfosuccinate will be essentially nonvolatile. Dioctyl sodium sulfosuccinate has
hydrolysis half-lives of 243 days at pH of 8 and 6.7 years at pH of 7. Aquatic
bioconcentration is not expected to be an important fate process, although
adsorption to sediment may be possible. Several studies have shown that dioctyl
sodium sulfosuccinate biodegrades rapidly.
Valorisation of the glycerol by-product from biodiesel

production
Jan C.J. Bart, ... Stefano Cavallaro, in Biodiesel Science and Technology, 2010
13.2 Industrial glycerol production

The terms glycerine, glycerin, and glycerol are used interchangeably although
slight differences exist in their definitions and use. Glycerol is the pure chemical
compound 1,2,3-propanetriol. Glycerine is the commonly used commercial name
for products whose principal component is glycerol. Glycerin refers to purified
commercial products containing 95% or more of glycerol. In this text we almost
invariably use ‘glycerol’ without distinction.
Almost all operations carried out in oleochemistry lead to the generation of the co-
product glycerol. This chemical has been obtained mainly by:
• pressurised hydrolysis of vegetable oils (fatty acids);
• transesterification (alcoholysis) of triglycerides (biofuels);
• saponification of triglycerides with alkali (soaps);
• chemical synthesis from C3 derivatives (petrochemicals); and
• controlled microbial fermentation of sugars, molasses and other carbohydrates.
The importance of these various routes has strongly varied with time. In fact, some
former starting materials for glycerol (such as epichlorohydrin) are nowadays being
proposed as glycerol products (see Section 13.5.7).
Following the emergence of synthetic detergents in the 1940s, soap manufacturing
from fatty acids was reduced and various synthetic processes for glycerol were
developed (by IG Farben, Degussa, Leuna, Shell, Olin Mathieson and others), based
mainly on allyl chloride (preferred; or its conversion product epichlorohydrin), allyl
alcohol and some other petrochemicals (Fig. 13.1). Nowadays, synthetic processes
for commercial production of glycerol account for only about 10% of global
production (see Table 13.1) and 25% of US production capacity (134 kt/yr).
13.1. Synthetic routes to glycerol.
Table 13.1. Global sources of glycerol production (2001) (after ref. [11])
Process Global production (%)
Fatty acids 41
Soap manufacture 21
Methyl esters for detergent alcohols 14
Methyl esters as biodiesel 11
Synthetic 9
Fermentation –
Other 4
Glycerol production by yeast fermentation has been known since Pasteur [9]. In
Saccharomyces cerevisiae (bakers’ yeast), glycerol is a by-product of the
fermentation of sugar to ethanol. Glycerol production by microbial fermentation is
unable to compete with chemical synthesis from petrochemical feedstocks due to
low glycerol yields and difficulty with extraction and purification of glycerol from
broth. Not surprisingly, the production cost of glycerol obtained by fermentation is
generally much higher than that of glycerol obtained from vegetable oils and fats.
Recently, significant improvements have been made in glycerol production from
glucose using osmotolerant yeasts on a (limited) commercial scale in China
(10 kt/yr). Glycerol production by microbial fermentation is reviewed in ref. [10].
Glycerol from renewable materials denotes a particular glycerol obtained during
conversions of fats or oils of plant or animal origin in general, such as
saponification or hydrolysis reactions, or else glycerol obtained in the production of
biodiesel by transesterification. Currently about 80% of US production and 90% of
global production are from natural glycerides. The primary sources of glycerol
include tallow (TLW), palm kernel oil (PKO) and coconut oil (CNO). Procter &
Gamble is the largest natural glycerol producer. Animal fats have been a main raw
material for glycerol. However, in view of BSE (bovine spongiform encephalopathy),
use of glycerol for human contact (food, pharmaceutical, cosmetics, etc.) nowadays
favours glycerol of vegetable origin.
Global glycerol production increased from 650 kt in 1995 to almost 900 kt in 2006,
of which 600 kt was from biodiesel production. Table 13.1 shows the global
production volume of natural and synthetic glycerol by source. In 2001, European
biodiesel production accounted for 11% of glycerol production or about 80 kt.
Before 1995, this source of glycerol was non-existent. In the past, US glycerol
production has oscillated in the range of 130 000–160 000 MT/yr. Nowadays, the
oleochemical (over)production of glycerol has greatly suppressed synthetic glycerol
and biodiesel glycerol production is becoming a major source. In 2007 US
biodiesel manufacturers produced 187 kt of crude glycerine, as compared to 150 kt
from other sources. The large surplus of glycerol by-product which entered the
chemical market has caused closure of existing glycerol plants.
Glycerol is now part of the fuel market, which has generated 800 kt of the product
in 2007. If the EU 2010 target is achieved, biodiesel demand could then increase to
9.8 Mt/yr (see Table 1.2), thus co-producing about 1 Mt/yr of glycerol. This quantity
exceeds the present total world consumption of glycerol. Moreover, if the US
replaces 2% of the on-road diesel with biodiesel by 2012, almost 333 kt/yr glycerol
would additionally be added to the market. This would rapidly saturate even the
current Chinese export market (about 0.1 Mt/yr). USDA-Foreign Agricultural
Service forecasts in June 2007 suggest an increase in glycerol from biodiesel
production by 2010 of over 167% from 2006.
Glycerol amounts typically to about 10% of the product output of a biodiesel fuel
(BDF) production process, although the yield depends on the feedstock
composition. For low FFA feedstocks (RSO, SBO, PMO, TLW, UCO) some 103.6–
108.9 t/ton feedstock is obtained, as compared to only 21.8 t glycerol/ton palm
fatty acid distillate (P-FAD) [12], (see Table 7.3). Most biodiesel companies (70%)
end up with a crude glycerin by-product. Some 20% is taking glycerin to technical
grade and only 5% pharmaceutical grade; burning is another outlet.
Although at present (2008) the global production of biodiesel is still fairly limited,
markets have already reacted strongly to the increased availability of this
polyalcohol with rapidly dropping prices which tend to destabilise the free market
for oleochemicals. At the same time, the excess market supply of glycerol in biofuel
and biolubricant applications could also easily set the biodiesel industry backwards.
Glycerol, produced in many countries, is now considered as a major platform
feedstock for a range of chemical processes (Fig. 13.2) and an important building
block for future biorefineries [13]. ADM, Ashland, BioMCN, Cargill, Dow, Senergy
Chemical, Solvay and others are set to produce glycerol-derived industrial products
such as methanol, ethylene glycol (EG), propylene glycol (PG) and epichlorohydrin
(ECH).
13.2. Glycerol chemistry.
Polymeric gels for diagnostics applications

Sławomir Wilczyński, Anna Stolecka-Warzecha, in Polymeric Gels, 2018
15.1.2 Composition
Water, glycerine, or alcohol can be used as coupling agents. The typical
composition of coupling hydrogels is presented in Table 15.1. These compounds,
however, have adverse application properties and their acoustic, thermal, and
viscoelastic properties are not conducive to using them.
Table 15.1. The typical composition of coupling hydrogels
Composition for 500 g of gel Amount (g)
Carbomer 10
Ethylenediaminetetraacetic acid 0.25
Propylene glycol 75
Trolamine 12.5
Water up to 500.0
As a consequence, gels are used most often as coupling agents. A distinction can
be made between hydrogels and lipogels (oleogels). Lipogels are usually composed
of lipophilic substances such as mineral, synthetic, or plant oils. Their use is limited
because they give the impression of viscosity on the skin and are difficult to
remove. Hydrogels, on the other hand, do not have these disadvantages and can be
easily removed from the skin without leaving any residue or greasy stains on
clothes (Lautenschläger, 2008). In addition, hydrogels, unlike lipogels, have no
negative effect on the plastic or rubber parts of the head (transducer) (Lutz and
Buscarini, 2013).
The procedure for preparing such a gel is as follows: dissolve
ethylenediaminetetraacetic acid in 400 g of water and add propylene glycol. Then
add the carbomer and mix with a high-speed stirrer to form a hydrogel without air
bubbles. In the last step, make up to 500 g with water (Lutz and Buscarini, 2013).
Hydrogels for diagnostic purposes are designed for short contact with tissues and
therefore belong to a group of products that can be defined as “rinse-off
characteristics.” Due to the high water content, hydrogels often contain
preservatives such as MDGN (1,2-dibromo-2,4-dicyanobutane). However,
preservatives, through the skin sonification, can bypass the skin barrier and cause
undesirable effects.
Hydrogels as couplers have proven their effectiveness in numerous studies (Bosch
et al., 2000). Hydrogels, other than the most common ones, i.e., carbomer and
propylene glycol, may also include polymers such as polyacrylamide (PAA). PAA-
based ultrasonic hydrogels can contain a lot of water—even over 90%, which
makes them easy and cheap to produce. In addition, their physicochemical
properties, such as viscoelasticity, can be easily modified by changing the
concentration of acrylamide monomer units. PAA is also characterized by very high
biocompatibility (Prokop et al., 2003).
Despite the fact that the common ultrasound gels are not expensive, their cost and
availability can pose challenges in developing countries. As a result, alternative
solutions based on other polymers, most often of natural origin, are proposed. One
such example is maize starch (Binkowski et al., 2014). Gels based on natural
ingredients neither imply worse image quality nor they pose a threat in the context
of skin irritation or risk of infection (Binkowski et al., 2014).
SEALANTS
George Wypych, in PVC Formulary (Second Edition), 2015
4.18 SINTERING
This is another technique used less frequently, but some patents can be found on
this subject, and these are reported below.
4.18.1 PATENTED INVENTIONS
Microporous material. [Data from Rainer, N. B., US Patent 6,569,495, May 27,
2003.]
Raw material Concentration, parts
Anhydrous glycerin 90
PVC emulsion (Vycar 351; 57.9 PVC) 150
Cellulose sponge cubes (1/2” size) 34.7
The mixture of glycerin and PVC emulsion is completely absorbed by sponge

cubes, which are further tumbled to achieve uniform distribution of liquid. The
impregnated cubes are exposed to 100°C for 30 min and at 127°C for 40 min,
which is sufficient to sinter particles of PVC. Glycerin is washed out by water in the
next step and cubes are dried. Cubes have a PVC/cellulose ratio of 3.41/1 and they
have a microporous structure. The cubes are used to remove toxic organic species
from water such as polychlorinated biphenyls, dioxins, polyaromatic hydrocarbons,
nitroaromatics, pesticides, herbicides, and volatile halocarbons.
Dust-free PVC. [Data from DiRienzo, D. J., US Patent 5,155,185, Oct. 13, 1992.]
Raw material Concentration, parts
PVC (Geon 143) 100
Dust-free mass resin 9
DIDP 45
Epoxidized soybean oil 5
Tin stabilizer (Mark 190) 4
This patent reports on special PVC developed by BFGoodrich (now PolyOne). Mass
polymerized resins are suitable in some application, including sintering, for which
the above formulation was used. Sintering process took 5 min at 232°C.
Battery separators. [Data from Riesberg, V.V., US Patent 4,252,756, Feb. 24, 1981.]
The goal of this invention is to produce battery separators which have porosity
greater than 50%. This porosity is required for electrolytic processes to occur. The
goal is achieved by mixing PVC powder with a pore-forming substance (e.g., 5%
NaHCO3) which, during the process of sintering at temperatures as high as 230°C,
undergoes degradation with formation of gas which helps to form the required
porosity. The technology and equipment are fully disclosed in the patent.
G
Richard P. Pohanish, in Sittig's Handbook of Toxic and Hazardous Chemicals and
Carcinogens (Sixth Edition), 2012
Short Term Exposure: Glycerin can be irritating to the eyes, skin, and respiratory
tract. When swallowed, it can cause insomnia, nausea, vomiting, diarrhea, fever,
hemoglobinuria, convulsions, and paralysis. Toxic in high concentrations; it is
somewhat dehydrating and irritating to exposed tissues. Symptoms include
headache, dizziness, insomnia, nausea, vomiting, diarrhea, fever, elevated blood
sugar, and diabetic coma; very large doses may cause irritation and dehydration of
tissues, hemolysis, renal failure, hemoglobinuria, convulsions, and paralysis.
Dry (CO2) Reforming
Jing Gao, ... Xiaoming Zheng, in Fuel Cells: Technologies for Fuel Processing, 2011
7.8.3 Glycerol
Glycerol, also called glycerin, is a sugar alcohol, which is a colorless, odorless,
viscous, sweet-tasting, low toxicity, water-soluble liquid. Glycerol is a by-product of
biodiesel manufacture. The biodiesel production for 2008 in EU27 and USA was
over 7.7 and 2.3 million metric tons, respectively. That is, more than 1.0 million
metric tons of glycerol was produced as a by-product. Currently disposal of surplus
glycerol is done by incineration. This has resulted in a market surplus of crude
glycerol typically containing 20% water and esterification catalyst residues. The
crude glycerol, however, can be purified and refined. Recently, much effort has
been made to convert glycerol to value-added molecules, such as conversion to
propylene glycol, acrolein, ethanol, and epichlorhydrin. In addition, it could be
used to produce hydrogen gas.
Thermal cracking of glycerol to CO and H2 can be performed easily, while this
cracking is an endothermic process that needs a huge energy input. In order to
decrease the amount of energy input, partial oxidation of glycerol to hydrogen
should be more favorable.
(7.58)
(7.59)
(7.60)
(7.61)
Kunkes et al. [206] reported in their study on the transformation of aqueous

glycerol solutions (30 and 80 wt%) over Pt/C, Re/C, and Pt-Re/C catalysts. They
found that the turnover frequencies of H2, CO, CO2, and light alkanes (methane,
ethane, and propane) increased with the addition of Re to Pt/C catalysts at 275 °C
and atmospheric pressure. The H2/CO ratio increased with the addition of Re,
demonstrating that Re improved the rate of water-gas shift reaction. Over Pt-Re/C
catalyst with an atomic ratio equal to 1, increasing pressure or decreasing
temperature caused the increasing of alkanes and light oxygenated hydrocarbons
(ethanol, methanol, propanediols, and acetone) at the cost of CO and CO2.
To our best knowledge, there are no papers on dry reforming of glycerol or partial
oxidation of glycerol to synthesis gas reported in the literature.
G
Richard P. Pohanish, in Sittig's Handbook of Toxic and Hazardous Chemicals and
Carcinogens (Seventh Edition), 2017
Short-Term Exposure: Glycerin can be irritating to the eyes, skin, and respiratory
tract. When swallowed, it can cause insomnia, nausea, vomiting, diarrhea, fever,
hemoglobinuria, convulsions, and paralysis. Toxic in high concentrations; it is
somewhat dehydrating and irritating to exposed tissues. Symptoms include
headache, dizziness, insomnia, nausea, vomiting, diarrhea, fever, elevated blood
sugar, and diabetic coma; very large doses may cause irritation and dehydration of
tissues, hemolysis, renal failure, hemoglobinuria, convulsions, and paralysis.
Other fuels for direct fuel cells (DFCs)

Alexandra M.F.R. Pinto, ... Daniela S. Falcão, in Direct Alcohol Fuel Cells for
Portable Applications, 2018
5.2.1 Basic principles

Glycerol, popularly known as glycerin, is a C3 alcohol with the chemical
formulation C3H8O3. Until the middle of the last century, glycerol was usually
obtained as a co-product of soap fabrication. More recently, an increasing interest
on biodiesel production, to replace the traditional diesel of petroleum, has
appeared and glycerol appears more as a co-product of biodiesel production (1 kg
of glycerol per 10 kg of biodiesel) [36]. In 2011, about 260,000 tons of glycerol were
produced as co-product of biodiesel fabrication in Brazil, corresponding to about 8
times more than the Brazilian demand of glycerol [36].
The reactions taking place on direct glycerol fuel cells, in acidic medium, are the
following:
Acidic medium
(5.16)
(5.17)
(5.18)
The DGFC could also be operated in alkaline medium. In this case, the reactions
occurring in cell are the following:
Alkaline medium
(5.19)
(5.20)
(5.21)
As referred for DEGFCs, although the overall reaction is the same for both cases,
the reactions occurring at the anode and cathode sides are different. Also, in
DGFCs, the glycerol crossover leads to performance and efficiency losses due to a
waste of fuel. This problem, as referred for DEGFCs, can be minimized by selecting
the operating conditions which generate lower values of glycerol crossover and/or
selecting catalysts more selective for ORR in the presence of glycerol. The working
principle similarity of a DGFC and a DEGFC is very high, with analogous reactions
occurring in both alkaline and acidic mediums, the only differences are on the fuel
used and the intermediate compounds formed. A scheme of the working principle
of a DGFC is displayed in Fig. 5.5. As reported for DEGFCs, the CO2 formed in the
oxidation reactions and the CO2 presented in the air lead to progressive
carbonation of the solution, implying the addition of alkali compounds like
potassium hydroxide or sodium hydroxide to guarantee alkaline conditions.
Fig. 5.5. Schematic illustration of a DGFC operating in (A) acidic medium and (B)
alkaline medium.
PLASTICIZERS USE AND SELECTION FOR SPECIFIC

POLYMERS
TERESHATOV V. VASILIY, ... MAKAROVA A. MARINA, in Handbook of Plasticizers
(Second Edition), 2012
11.61.2 PRACTICAL CONCENTRATIONS

• glycerin: 0.1–5 wt%,814 0.5 wt%,830 2 wt%,818 3–7 wt%,807 10–40 wt%,811 16.9
wt%,803 15–30 wt%,831 33 wt%,794 or 25–75 wt%806
• vegetable oils: 0.1 wt%,792 0.5%,804 or 6.25 wt%829
• sorbitol: 35 wt%827
• tributyl acetyl citrate: 3 wt%815
• triacetin: 5–25 wt%825
• diethylene glycol dibenzoate and dipropylene glycol dibenzoate 50/50 weight

blend: 2–30 wt%831
• poly(ethylene glycol): 30–40 wt%787
• polyester plasticizer: 5–25 wt%,788, 816, 819 33 phr,788 or 57 phr786
Copyright © 2020 Elsevier B.V. or its licensors or contributors.

ScienceDirect ® is a registered trademark of Elsevier B.V.

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31/1/2020 Glycerol - an overview | ScienceDirect Topics

Biodiesel, Transesteriﬁcation, Hydrogen, Viscosity, Feedstocks, Glycerols,

Pyrolysis of Alcohols and Phenols

Table 4.1.11. Identiﬁcation of the Main Peaks in the Chromatogram Shown in

2 Water 5.20–7.05 18 7732- 75.77

3 1-Hydroxy-2-propanone 22.19 74 116- 0.36

4 2-Butoxyethanol 31.10 118 111- 0.38

5 Glycerin 41.02 92 56-81- 23.25

6 2,2,-Dimethyl-1,3-dioxolane-4- 44.13 132 14347- 0.11

7 2,2,-Dimethyl-1,3-dioxolane-4- 44.49 132 - 0.13

Pyrolysis of 2 mg of glycerin at higher temperature of 850°C generates the

Fig. 4.1.13. Pyrogram of glycerin at 850°C. Peak assignment is given in Table

Table 4.1.12. Identiﬁcation of the Main Peaks in the Chromatogram Shown in

2 Formaldehyde 4.50 30 50-00- 4.93

3 Water 5.30 18 – 5.29

4 Acetaldehyde 5.66 44 75-07- 7.09

5 2-Propenal (acrolein) 8.35 56 107- 9.47

6 2-Oxopropanal (glyoxal) 9.15 72 78-98- 0.18

7 2-Propen-1-ol 12.93 58 107- 2.08

8 Hydroxyacetaldehyde 17.25 60 141- 0.63

9 2-Ethoxypropane 19.27 88 625- 0.40

10 Acetic acid 19.99 60 64-19- 0.22

11 1-Hydroxy-2-propanone 22.20 94 116- 4.63

12 Acetoin 24.04 88 513- 0.07

13 Propanoic acid 25.01 74 79-09- 0.04

14 Glycidol 25.56 74 556- 2.75

15 Propylene glycol 27.98 76 57-55- 0.26

16 Unknown 30.62 74 – 0.05

17 2-Methyl-4-methylol-1,3- 32.65 118 – 0.11

18 4-Methanol-1,3-dioxolane 32.93 104 86687- 0.07

19 5-Methyl-3,6,8- 33.22 130 30120- 0.03

20 trans-4-Hydroxymethyl-2- 33.78 118 – 0.06

21 2-Vinyl-1,3-dioxolane-4- 36.98 130 4313- 0.06

22 2-Vinyl-1,3-dioxolane-4- 37.71 130 – 0.05

23 Glycerin 42.40 92 56-81- 60.92

24 2,2,-Dimethyl-1,3-dioxolane-4- 44.13 132 14347- 0.29

25 2,2,-Dimethyl-1,3-dioxolane-4- 44.58 132 – 0.32

Note: Bold numbers indicate large component in the pyrolyzate.

Acetaldehyde also can be generated directly from glycerin by radical reactions, as

One potential application of glycerin pyrolysis is the production of combustible gas

HEALTH, SAFETY AND ENVIRONMENTAL ISSUES

16.2.4 OTHER CHEMICAL COMPOUNDS

Valorisation of the glycerol by-product from biodiesel

13.2 Industrial glycerol production

13.1. Synthetic routes to glycerol.

Process Global production (%)

Methyl esters for detergent alcohols 14

Methyl esters as biodiesel 11

13.2. Glycerol chemistry.

Polymeric gels for diagnostics applications

Table 15.1. The typical composition of coupling hydrogels

Composition for 500 g of gel Amount (g)

Ethylenediaminetetraacetic acid 0.25

Raw material Concentration, parts

PVC emulsion (Vycar 351; 57.9 PVC) 150

Cellulose sponge cubes (1/2” size) 34.7

The mixture of glycerin and PVC emulsion is completely absorbed by sponge

Raw material Concentration, parts

PVC (Geon 143) 100

Dust-free mass resin 9

Epoxidized soybean oil 5

Tin stabilizer (Mark 190) 4

Dry (CO2) Reforming