Development of structured reactors for transformation of biomass components to high-value products

1. Development of structured reactors for transformation of biomass components to high-value products – green process intensification

V.V. Shumilov, D.Yu. Murzin, T. Salmi
Laboratory of Industrial Chemistry and Reaction Engineering
Abo Akademi University, 20500 Turku, Finland
Levulinic acid/Levulinic acid esthers
Levulinic acid is a well-known
product of hexose acid
hydrolysis. It is used as a precursor
for pharmaceuticals, plasticizers and various other additives.
Besides that, it is recognized as a building block or starting
material for a wide number of compounds. This family addresses
a number of large volume chemical markets. For example,
potential biofuels including γ-Valerolactone, 2-Methyl-THF,
ethyl levulinate. Levulinic acid is an attractive starting material
in producing 5-carbon compounds. This study relates also to use
of levulinic acid ester as a starting material.
Ethyl levulinate may be
produced from wheat straw, for
example, by direct conversion in
ethanol media
Reductive
amination
process for preparing aryl or alkyl
A
and cycloalkyl
pyrrolidones utilizing ethyl levulinate and aryl or alkyl
amines. .
I – ethyl levulinate
II – 3-aminopropanol
III – 5-methyl-N-(3-hydroxypropyl)-2-pyrrolidone
Pyrrolidones
Pyrrolidones that could be produced through this reaction may be
used in pharmaceutical formulations (5-methyl-N-hydroxyethyl-2pyrrolidone),
cleaning
compositions
(5-Methyl-N-octyl-2pyrrolidone, 5-Methyl-N-dodecyl-2-pyrrolidone, 5-Methyl-Ndecyl-2-pyrrolidone), stripping/cleaning formulation (5-Methyl-Nmethyl-2-pyrrolidone), agrochemical compositions (5-Methyl-Nalkyl pyrrolidone), protective composition for painted automobile
surfaces (5-Methyl-N-octyl-2-pyrrolidone) [1]
Transmission Electron Microscopy
Н2 + I + II +
solvent
(dioxane or
water)
Sample with a smooth surface.
Smooth surface comes from αalumina
Sample with a rough surface.
Rough surface corresponds to
γ-alumina
Aryl and alkyl amines
Aryl and alkyl amines represent the compound with formula
R—NH2 wherein R is an alkyl group which has from 1 to 30
carbons, or R may be C1-C30 unsubstituted or substituted
alkyl, C1-C30 unsubstituted or substituted alkenyl, C1-C30
unsubstituted or substituted alkynyl, C3-C30 unsubstituted
or substituted cycloalkyl, or C1-C30 unsubstituted or
substituted cycloalkyl containing at least one heteroatom or
R may be an aromatic group.
Examples of compounds that could be used:
Reactor
Alkyl Amine:
Aryl Amine:
III
Cyclohexylamine
Aniline
Pentylamine
2-Ethyl Aniline
Reaction conditions:
t-Octylamine
o-Toluidine
T = 75 … 225°C
Ethanolamine
4-Ethyl Aniline
P = 1 … 2.5 MPa
3-Aminopropanol
2-Isopropyl Aniline
Cyclopentylamine
2-Phenethylamine
Cycloheptylamine
p-Toluidine
Development
of
[1]
o-Anisidine
Coating of the polyurethane sponge with α-alumina slurry
Highly porous ceramic structures can be produced in various forms from a
variety of materials exhibiting such properties as high porosity and good
interconnectivity. Due to their specific geometry and other features these materials
can be used in a wide range of engineering applications. In this study a
polyurethane matrix replica method was used for the production of highly porous
cellular materials.
Ru nanoparticles
a macroporous ceramic catalytic system
Adding of an active catalytic component
Surface area enlargement
α-alumina
γ-alumina
Ru was deposited by a kind of incipient wetness impregnation
technique, where carrier samples are inserted in Petri Dish that
contains Ru Nytrosyl Nitrate solution with calculated amount of Ru
which has been drained up in porous structure by capillary action. Salt
solution can also be added dropwise.
Deposition of
Ru Nytrosyl
Nitrate salt
solution
SA before procedure SA after procedure
Method consist of adding the additional
layer of γ-alumina slurry on the surface of
the foam. Allowed to add up to 30 wt.% of
γ-alumina
on
the
foam
walls.
Simultaneously, the mechanical strength
PU sponges covered with
α-alumina carriers
Polyurethane (PU) sponges
increased, while the pores became less
corundum
interconnective.
Alumina in the α phase is the strongest and the hardest of oxide ceramics. Its
The other method comprised of immersing
hardness, refractoriness, wearability resistance properties, dielectric and good thermal
α-alumina support foams or samples coated
properties make it suitable for a wide application range. Thermally stable α-alumina
with γ-alumina in a hot (75-85°C) solution
(corundum) has a trigonal structure (R-3c) with ABAB stacking of oxygen planes
of
aluminium
nitrate,
in
which
along the c-direction with Al (III) in 2/3 of the octahedral interstitial positions.
sedimentation of γ-alumina occurred. Two
immersions for 1 min each were sufficient
Conclusions: α-alumina foams have been synthesized by the replica method. to increase the mass of the sample for
Washscoating of them with γ –alumina and subsequent impregnation with Pt roughly 5 wt.%.
and Ru resulted in active catalytic system creation.
Deposition of
Pt from
hexachloropl
atinic acid
Drying
NaOH
Set-up for the
deposition of Pt
on carrier
surface
Reduction
in flowing Н2
Reduction
in flowing Н2
Set-up for the
reduction in
flowing Н2
Deposition of an Pt was performed by impregnation with a water
solution of hexachloroplatinic acid. Cl has to be removed for ensuring
catalytic activity. Can be used in hydrogenation reactions like selective
hydrogenation of sugars
References: Leo Ernest Manzer, Wilmington, DE (Us), «Production of 5-methyl-n-aryl-2-pyrrolidone and 5-methyl-n-alkyl-2-pyrrolidone by
reductive amination of levulinic acid esters with aryl and alkyl amines», US 2005/0038265 A1, Feb. 17,2005