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
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.
Alumina in the α phase is the strongest and the hardest of oxide ceramics. Its hardness, refractoriness, wearability resistance properties, dielectric and good thermal properties make it suitable for a wide application range. Thermally stable α-alumina (corundum) has a trigonal structure (R-3c) with ABAB stacking of oxygen planes along the c-direction with Al (III) in 2/3 of the octahedral interstitial positions.
Deposition of Pt from hexachloroplatinic acid
NaOH
Reduction
in flowing Н2
Set-up for the reduction in flowing Н2
Set-up for the deposition of Pt on carrier surface
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 increased, while the pores became less interconnective.
The other method comprised of immersing α-alumina support foams or samples coated with γ-alumina in a hot (75-85°C) solution of aluminium nitrate, in which sedimentation of γ-alumina occurred. Two immersions for 1 min each were sufficient to increase the mass of the sample for roughly 5 wt.%.
Conclusions: α-alumina foams have been synthesized by the replica method. Washscoating of them with γ –alumina and subsequent impregnation with Pt and Ru resulted in active catalytic system creation.
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
Levulinic acid/Levulinic acid esthers
Pyrrolidones
Surface area enlargement
Coating of the polyurethane sponge with α-alumina slurry
Aryl and alkyl amines
Transmission Electron Microscopy
Sample with a smooth surface. Smooth surface comes from α-alumina
Sample with a rough surface.
Rough surface corresponds to γ-alumina
Ru nanoparticles
Reactor
Adding of an active catalytic component
A process for preparing aryl or alkyl and cycloalkyl pyrrolidones utilizing ethyl levulinate and aryl or alkyl amines. .
Development of a macroporous ceramic catalytic system
SA before procedure
SA after procedure
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
Deposition of Ru Nytrosyl Nitrate salt solution
Drying
Reduction
in flowing Н2
I – ethyl levulinate
II – 3-aminopropanol
III – 5-methyl-N-(3-hydroxypropyl)-2-pyrrolidone
Reductive amination
Н2 + I + II + solvent (dioxane or water)
Reaction conditions:
T = 75 … 225°C
P = 1 … 2.5 MPa
III
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:
Aryl Amine:
Aniline
2-Ethyl Aniline
o-Toluidine
4-Ethyl Aniline
2-Isopropyl Aniline
2-Phenethylamine
p-Toluidine
o-Anisidine
Alkyl Amine:
Cyclohexylamine
Pentylamine
t-Octylamine
Ethanolamine
3-Aminopropanol
Cyclopentylamine
Cycloheptylamine
[1]
Pyrrolidones that could be produced through this reaction may be used in pharmaceutical formulations (5-methyl-N-hydroxyethyl-2-pyrrolidone), cleaning compositions (5-Methyl-N-octyl-2-pyrrolidone, 5-Methyl-N-dodecyl-2-pyrrolidone, 5-Methyl-N-decyl-2-pyrrolidone), stripping/cleaning formulation (5-Methyl-N-methyl-2-pyrrolidone), agrochemical compositions (5-Methyl-N-alkyl pyrrolidone), protective composition for painted automobile surfaces (5-Methyl-N-octyl-2-pyrrolidone) [1]
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
