http://articles.extension.

org/pages/29264/new-uses-for-crude-glycerin-from-biodiesel-production

Converting crude glycerol into valued-added products

Converting crude glycerol into valued-added products through thermo-chemical methods or

biological methods is an alternative for utilizing this waste stream. It has been reported that
glycerol can be thermochemically converted into propylene glycol (Dasari et al. 2005; Alhanash
et al. 2008), acetol (Chiu et al. 2006), or a variety of other products (Johnson & Taconi 2007).
Cortright et al. (2002) have developed an aqueous phase reforming process that transforms
glycerol into hydrogen. Virent Energy Systems is currently trying to commercialize this
technology and claim that sodium hydroxide, methanol, and high pH levels within crude glycerol
help the process (Nilles 2005).

Glycerol can also be converted to citric acid by the yeast Yarrowia lipolytica. It has been
reported that this organism produces the same amount of citric acid when grown on glucose or
on raw glycerol (Papanikolaou & Aggelis 2002).

Clostridium butyricum can utilize biodiesel-derived glycerol to produce 1,3-propanediol (an

important chemical building block with many industrial uses) in both batch and continuous
cultures

http://biodiesel.org/reports/20110501_gen-427l.pdf

The glycerol side stream typically contains a mixture of glycerol, methanol, water, inorganic salts
(catalyst residue), free fatty acids, unreacted mono-, di-, and triglycerides, methyl esters, and a variety
of other matter organic non-glycerol (MONG) in varying proportions. The methanol is typically
stripped from this stream and reused, leaving crude glycerol after neutralization. In its raw state crude
glycerol has a high salt and free fatty acid content and a substantial color (yellow to dark brown).
Consequently, crude glycerol has few direct uses, and its fuel value is also marginal. An economic
solution for the purification of crude glycerol streams combines electrodialysis and nanofiltration,
affording a colorless liquid with low salt content, equivalent to technical grade purity (Figure 1.11).21
The recovered glycerol, after polishing if necessary using ion exchange and removal of watermethanol
solution by evaporation, easily meets USP glycerol standards. This membranebased technique avoids
expensive evaporation and distillation, and also such problems as foaming, carry-over of contaminants,
and limited recovery

Rationale

Glycerol occurs as a waste product in the biodiesel industry

In the synthesis of biodiesel via the transesterification of vegetable oils, 10 wt% of glycerol is obtained
as byproduct. This means that, by increasing the biodiesel production, the glycerol availability also
increases and its cost goes down more and more. In order to consume the large amount of glycerol
derived from biodiesel production in a profitable way, only two strategies are possible: (i) use glycerol as
raw material to produce fuel additives and (ii) use glycerol as raw material to produce commodities. In
the present work, we have briefly considered the first aspect while focusing, in particular, on the second
opportunity by reviewing the production of chlorohydrins by glycerol hydrochlorination with HCl.
Chlorohydrins are important intermediates in the production of epichlorohydrin used to produce epoxy
resins. The advantages of producing chlorohydrins by starting from glycerol instead of propenethat is,
the classical routewill be discussed. The glycerol hydrochlorination reaction is catalyzed by carboxylic
acids, and in this work, we describe (i) the reaction conditions normally adopted; (ii) the behavior of
different catalysts proposed in the literature (concerning activity and selectivity); (iii) the reaction
mechanism; (iv) the kinetic laws, reported by different authors, along with the related parameters; and
(v) the role of mass transfer. A brief discussion on the best reactors for performing the reaction and
some information about the different processes used to produce epichlorohydrin starting from glycerol
will also be reported. Some catalysts, other than carboxylic acids, have also been briefly reviewed,
although they have not been used in industrial plants until recently.