Recycled PMMA prepared directly from crude MMA obtained from thermal depolymerization of mixed PMMA waste.

Recycled PMMA was prepared by directly polymerizing crude pyrolysis oils from lab-scale pyrolysis of collected industrial waste PMMA. The pyrolysis oils consisted mainly of methyl methacrylate (MMA, >85%), while the type and number of by-products from the thermal process were assigned through GC-MS analysis showing a clear correlation to the pyrolysis temperature. By-products can be removed by distillation; however, directly employing the crude oils to prepare PMMA through solution, suspension, emulsion, or casting polymerization was investigated to assess the potential for omitting this costly step. It was found that the crude pyrolysis oils could be polymerized efficiently via solution, emulsion, and casting polymerization to produce a polymer similar to the PMMA prepared from a pristine monomer. The impurities in the PMMAs prepared from the crude mixtures were investigated by extraction analyses followed by screening by GC-MS. In the case of casting polymerization, the GC-MS analysis, as expected, revealed various residual by-products, while solution and emulsion polymerization showed only very few impurities, mainly originating from the polymerization and not the feed material. Additional purification of the crude pyrolysis oils would be required for applications in casting polymerization. In contrast, direct polymerization by emulsion or solution polymerization is considered applicable for producing pristine PMMA from crude waste PMMA pyrolysis oil.

Kinetics based reaction optimization of enzyme catalyzed reduction of formaldehyde to methanol with synchronous cofactor regeneration.

Enzymatic reduction of carbon dioxide (CO2 ) to methanol (CH3 OH) can be accomplished using a designed set-up of three oxidoreductases utilizing reduced pyridine nucleotide (NADH) as cofactor for the reducing equivalents electron supply. For this enzyme system to function efficiently a balanced regeneration of the reducing equivalents during reaction is required. Herein, we report the optimization of the enzymatic conversion of formaldehyde (CHOH) to CH3 OH by alcohol dehydrogenase, the final step of the enzymatic redox reaction of CO2 to CH3 OH, with kinetically synchronous enzymatic cofactor regeneration using either glucose dehydrogenase (System I) or xylose dehydrogenase (System II). A mathematical model of the enzyme kinetics was employed to identify the best reaction set-up for attaining optimal cofactor recycling rate and enzyme utilization efficiency. Targeted process optimization experiments were conducted to verify the kinetically modeled results. Repetitive reaction cycles were shown to enhance the yield of CH3 OH, increase the total turnover number (TTN) and the biocatalytic productivity rate (BPR) value for both system I and II whilst minimizing the exposure of the enzymes to high concentrations of CHOH. System II was found to be superior to System I with a yield of 8 mM CH3 OH, a TTN of 160 and BPR of 24 µmol CH3 OH/U · h during 6 hr of reaction. The study demonstrates that an optimal reaction set-up could be designed from rational kinetics modeling to maximize the yield of CH3 OH, whilst simultaneously optimizing cofactor recycling and enzyme utilization efficiency.

Changes imposed by pyrolysis, thermal gasification and incineration on composition and phosphorus fertilizer quality of municipal sewage sludge.

Fertilizer quality of ash and char from incineration, gasification and pyrolysis of a single municipal sewage sludge sample were investigated by comparing composition and phosphorus (P) plant availability. A process for post oxidation of gasification ash and pyrolysis char was developed and the oxidized materials were investigated as well. Sequential extraction with full elemental balances of the extracted pools as well as scanning electron microscopy with energy dispersive X-ray spectroscopy were used to investigate the mechanisms driving the observed differences in composition and P plant availability in a short-term soil incubation study. The compositional changes related mainly to differences in the proximate composition as well as to the release of especially nitrogen, sulfur, cadmium and to some extent, phosphorus (P). The cadmium load per unit of P was reduced with 75-85% in gasification processes and 10-15% in pyrolysis whereas no reduction was observed in incineration processes. The influence on other heavy metals was less pronounced. The plant availability of P in the substrates varied from almost zero to almost 100% of the plant availability of P in the untreated sludge. Post-oxidized slow pyrolysis char was found to be the substrate with the highest P fertilizer value while ash from commercial fluid bed sludge incineration had the lowest P fertilizer quality. The high P fertilizer value in the best substrate is suggested to be a function of several different mechanisms including structural surface changes and improvements in the association of P to especially magnesium, calcium and aluminum.

Low temperature circulating fluidized bed gasification and co-gasification of municipal sewage sludge. Part 1: Process performance and gas product characterization.

Results from five experimental campaigns with Low Temperature Circulating Fluidized Bed (LT-CFB) gasification of straw and/or municipal sewage sludge (MSS) from three different Danish municipal waste water treatment plants in pilot and demonstration scale are analyzed and compared. The gasification process is characterized with respect to process stability, process performance and gas product characteristics. All experimental campaigns were conducted at maximum temperatures below 750°C, with air equivalence ratios around 0.12 and with pure silica sand as start-up bed material. A total of 8600kg of MSS dry matter was gasified during 133h of operation. The average thermal loads during the five experiments were 62-100% of nominal capacity. The short term stability of all campaigns was excellent, but gasification of dry MSS lead to substantial accumulation of coarse and rigid, but un-sintered, ash particles in the system. Co-gasification of MSS with sufficient amounts of cereal straw was found to be an effective way to mitigate these issues as well as eliminate thermal MSS drying requirements. Characterization of gas products and process performance showed that even though gas composition varied substantially, hot gas efficiencies of around 90% could be achieved for all MSS fuel types.

Mechanistic aspects of the nucleophilic substitution of pectin. On the formation of chloromethane.

Chloromethane, accounting for approximately 16% of the tropospheric chlorine, is mainly coming from natural sources. However anthropogenic activities, such as combustion of biomass may contribute significantly as well. The present study focuses on the thermal solid state reaction between pectin, an important constituent of biomass, and chloride ions as found in alkali metal chlorides. The formation of chloromethane is evident with the amount formed being linear with respect to chloride if pectin is in great excess. Thus the reaction is explained as a pseudo first order SN2 reaction between the chloride ion and the methyl ester moiety in pectin. It is suggested that the polymeric nature of pectin plays an active role by an enhanced transport of halides along the carbohydrate chain. Optimal reaction temperature is around 210°C. At higher temperatures the yield of chloromethane decreases due to a thermal decomposition of the pectin. The possible influence of the type of cation is discussed.

Composite films of arabinoxylan and fibrous sepiolite: morphological, mechanical, and barrier properties.

Hemicelluloses represent a largely unutilized resource for future bioderived films in packaging and other applications. However, improvement of film properties is needed in order to transfer this potential into reality. In this context, sepiolite, a fibrous clay, was investigated as an additive to enhance the properties of rye flour arabinoxylan. Composite films cast from arabinoxylan solutions and sepiolite suspensions in water were transparent or semitransparent at additive loadings in the 2.5-10 wt % range. Scanning electron microscopy showed that the sepiolite was well dispersed in the arabinoxylan films and sepiolite fiber aggregation was not found. FT-IR spectroscopy provided some evidence for hydrogen bonding between sepiolite and arabinoxylan. Consistent with these findings, mechanical testing showed increases in film stiffness and strength with sepiolite addition and the effect of poly(ethylene glycol) methyl ether (mPEG) plasticizer addition. Incorporation of sepiolite did not significantly influence the thermal degradation or the gas barrier properties of arabinoxylan films, which is likely a consequence of sepiolite fiber morphology. In summary, sepiolite was shown to have potential as an additive to obtain stronger hemicellulose films although other approaches, possibly in combination with the use of sepiolite, would be needed if enhanced film barrier properties are required for specific applications.

Carbohydrate analysis of hemicelluloses by gas chromatography-mass spectrometry of acetylated methyl glycosides.

A method based on gas chromatography-mass spectrometry analysis of acetylated methyl glycosides was developed in order to analyze monosaccharides obtained from various hemicelluloses. The derivatives of monosaccharide standards, arabinose, glucose, and xylose were studied in detail and (13)C-labeled analogues were used for identification and quantitative analysis. Excellent chromatographic separation of the monosaccharide derivatives was found and identification of the anomeric configuration was feasible through a prepared and identified pure methyl 2,3,4,6-tetra-O-acetyl-ß-D-glucopyranoside. The electron ionization mass spectrum and fragmentation path was studied for each monosaccharide derivative. Fragment ion pairs of labeled and unlabeled monosaccharides were used for quantification; m/z 243/248 for glucose, 128/132 for xylose, and 217/218 for arabinose. Using the intensity ratios obtained from the extracted ion chromatograms, accurate quantification of monosaccharide constituents of selected hemicelluloses was demonstrated.