The Catalyst Review - October 2015 - 4

PROCESS NEWS

Putting More 'Bio' Into Catalyst Converts Strong C-H Bonds to Amines
Biodiesel Fuels...
Selectively...
Biodiesel fuels are made by the
transesterification of plant-derived
triglycerides, a process that generates
impure glycerin as a byproduct while
consuming fossil-fuel-derived methanol.
Although there have been efforts in
recent years to utilize the large volumes
of glycerin byproduct, most of these
efforts focused on cleaning up the glycerin
for applications in pharmaceuticals and
cosmetics, or converting it into other
commodity chemicals, such as propylene
glycol, epichlorohydrin, and acrolein.
Now, chemists from the Cardiff Catalyst
Institute, School of Chemistry at Cardiff
University (UK) have discovered a way
to turn crude glycerin into methanol,
which can then be fed back to the
transesterification process. Recycling the
glycerin as methanol can increase the
biodiesel fuel production by an estimated
10%, says professor Graham Hutchings,
director of the institute. In contrast to
other processes that hydrogenate glycerin
into methanol using H2 at high pressure,
the Cardiff method uses water as the
source of hydrogen atoms, he explains.
The researchers demonstrated that
glycerin (10-30 vol.% aqueous solution)
reacts with water over a magnesiumoxide catalyst to give methanol with
high yields (25% conversion, 40%
selectivity). The gas-phase reaction is
carried out in a conventional packed-bed
reactor at temperatures of 523-680K
and atmospheric pressure-much
milder conditions than the so-called
Supermethanol concept, which integrates
gylcerin conversion into synthesis
gas production (reforming conditions
24-27 MPa, 950-1,000K) with methanol
synthesis (24-27 MPa, 470-520K).
Although the work is still in the early
stages, Hutchings says the discovery offers
good opportunity to optimize biodiesel
production while making it possible to
produce fatty acid methyl ester (FAME)
with 100% renewable content. The
researchers plan to optimize the catalyst
to significantly increase its activity and
selectivity. Source: Chemical Engineering,
10/2015, p. 8.
4

An inexpensive manganese compound solves a common problem for catalysts-the
tendency of many to be highly reactive or selective but not both. The manganese
catalyst can aminate strong C-H bonds but doesn't interfere with other reactive
groups. Some previously reported precious-metal catalysts are reactive enough to
aminate the most recalcitrant C-H bonds, such as primary ones, but they are expensive,
toxic, and tend to lack selectivity, oxidizing other functional groups such as olefins
simultaneously. Meanwhile, inexpensive and nontoxic iron-based catalysts are usually
too weak to convert strong C-H bonds to amines. Now M. Christina White of the
University of Illinois, Urbana-Champaign, and coworkers report that a Mn(III)-tertbutylphthalocyanine/antimony-hexafluoride complex not only aminates these stubborn
bonds but does so selectively in the presence of olefins. To carry out the reaction, the
chemists first convert a molecule's alcohol group to a sulfamate, a sulfur- and nitrogencontaining ester. The Mn catalyst and an oxidizing reagent then activate the sulfamate
so it attacks a C-H one or two bonds away, yielding a cyclic sulfamate. Sulfamate ester
rings can then be opened to yield diamines, amino alcohols, or other products. The
researchers used the synthesis to carry out late-stage C-H aminations of seven complex
alcohol-containing substrates, including betulinic acid, a natural product with anticancer
activity. White's group synthesized the Mn catalyst in one step from commercial
materials, and the University of Illinois has licensed it to Aldrich, which is making it
available commercially. Source: Chemical & Engineering News, 10/2015, p. 8.

This Cobalt-based Catalyst
is Less Expensive, More
Active Than Its Rhodium You are
Analog...
Researchers from Hokkaido University (Japan)
in collaboration with Hoshi University (Japan)
has developed an inexpensive cobalt-based
catalyst that can synthesize useful chemicals
with fewer reaction steps and reduced waste
generation compared to the analogous
rhodium-based catalyst. The new catalyst
is a metal complex of Co(III) with the ligand
1,2,3,4,5-pentamethylcyclopentadienyl (Cp*),
designated as [Cp*CoIII]. The researchers
demonstrated the unique reactivity of a
[Cp*CoIII] catalyst over analogous [Cp*RhIII]
catalyst for the C-H allylation reaction with
allyl alcohols in dichloroethane (DCE). After
8 h at 60°C, a cationic [Cp*CoIII] catalyst
promoted the direct, dehydrative C-H
allylation with non-activated allyl alcohols
to give C2-allylated indoles, pyrrole and
1-phenyl-pyrazole with good yields. Analogous
[Cp*RhIII] catalysts were not effective.
Allylated products were obtained with high
γ-selectivity in 62-99 % yield, and good
turnover numbers of up to 62, were observed.
Source: Chemical Engineering, 10/2015, p. 8.

Invited...
To learn about Idaho National
Laboratory's Advanced Manufacturing
Group and its research at the upcoming
AIChE annual meeting November 12,
2015 in Salt Lake City, Utah. Join us in
Room 250D at the Salt Palace Convention
Center for two workshops:
Workshop #1 - Efficient Manufacturing,
Better Industrial Catalysts: Shifting the
Focus to Composition/Kinetics
Workshop #2 - Energy-Water Nexus

The Catalyst Review

For additional details contact:
kortny.rolston-duce@inl.gov

October 2015

The Catalyst Review - October 2015

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