Mark J. Gronnow

Direct Microwave-Assisted Hydrothermal Depolymerization of Cellulose

A systematic investigation of the interaction of microwave irradiation with microcrystalline cellulose has been carried out, covering a broad temperature range (150 → 270 °C). A variety of analytical techniques (e.g., HPLC, (13)C NMR, FTIR, CHN analysis, hydrogen-deuterium exchange) allowed for the analysis of the obtained liquid and solid products. Based on these results a mechanism of cellulose interaction with microwaves is proposed. Thereby the degree of freedom of the cellulose enclosed CH2OH groups was found to be crucial. This mechanism allows for the explanation of the different experimental observations such as high efficiency of microwave treatment; the dependence of the selectivity/yield of glucose on the applied microwave density; the observed high glucose to HMF ratio; and the influence of the degree of cellulose crystallinity on the results of the hydrolysis process. The highest selectivity toward glucose was found to be ~75% while the highest glucose yield obtained was 21%.

A novel highly active biomaterial supported palladium catalyst

We have developed an expanded starch supported palladium catalyst which is highly active in Suzuki, Heck and Sonogashira reactions.

Microwave-mediated pyrolysis of macro-algae

Macro-algae (seaweed) is an abundant and, for the most part, under-utilised resource. This study has shown that microwave (MW)-mediated pyrolysis of seaweed occurs at extremely low temperatures and produces chemical rich bio-oils which are rich in aromatics, sugars and other high value chemicals.

From waste to wealth using green chemistry

The availability of chemically rich food supply chain waste (FSCW) gives it considerable potential as a resource for the manufacture of chemicals including materials and fuels. By applying clean chemical technologies to the extraction and conversion of molecules from FSCW, we can aim to produce genuinely green and sustainable products to help meet the legislative and consumer-oriented demands of a sustainable society. Low-temperature microwave (MW) processing is a particularly powerful technology to achieve this aim and is shown to be effective for several different high-volume, geographically diverse biomass types.

Low temperature microwave-assisted vs conventional pyrolysis of various biomass feedstocks

Abstract A comparison between conventional pyrolysis and a novel developed low-temperature microwave-assisted pyrolysis methodology has been performed for the valorisation of a range of biomass feedstocks including waste residues. Microwave pyrolysis was found to efficiently deliver comparable evolution of bio-gases in the system as compared with conventional pyrolysis at significantly reduced temperatures (120–180°C vs 250–400°C). The gas obtained from microwave-assisted pyrolysis was found to contain CO 2 , CH 4 and CO as major components as well as other related chemicals (e.g. acids, aldehydes, alkanes) which were obtained in different proportions depending on the selected feedstock.

Low-temperature microwave-assisted pyrolysis of waste office paper and the application of bio-oil as an Al adhesive

The conversion of waste office paper (printed or photocopied) to bio-oil via low temperature (<200 °C) microwave-assisted pyrolysis, and its utilisation as an adhesive for aluminium–aluminium bonding are reported. The yields for the organic and aqueous phase bio-oil are 19% and 23%, respectively. The pyrolysis products were characterized by ICP-MS, ATR-IR, GC-MS and NMR to reveal broad categories of compounds indicative of sugars (carbohydrates), aromatics and carbonyl-containing moieties. Application of the organic phase bio-oil (70 mg) to Al plates (50 mm × 50 mm) followed by curing at different temperatures and time periods revealed that a maximum tensile strength of approximately 2300 N could be attained at 160 °C for 8 h cure. Also, at a fixed temperature, the tensile strength increased with increasing curing time. To gain an in-depth understanding of the adhesive properties of bio-oil, a liquid–liquid fractionation of the organic phase bio-oil was conducted. The ‘acidic’ fraction showed far better adhesion properties than the ‘neutral’ fraction with no bonding achieved for the aqueous fraction. A combination of the ‘acidic’ and ‘neutral’ fraction gave better adhesion, thus suggesting a possible synergistic or co-operative effect.

Torrefaction/biochar production by microwave and conventional slow pyrolysis – comparison of energy properties

The energy efficiency of torrefaction/pyrolysis of biomass to fuel/biochar was studied using conventional (slow) and microwave (low temperature) pyrolysis. Conventional pyrolysis is approximately three times as energy efficient as microwave pyrolysis, in terms of the energy required to process a unit of feedstock. However, this is more than compensated for by the higher energy content of the condensable and gaseous coproducts from microwave pyrolysis, as these can be utilized to generate the electricity required to drive the process. It is proposed that the most efficient method of torrefaction/biochar production is a combination of conventional heating with ‘catalytic’ amount of microwave irradiation.

PCDDs, PCDFs and PCNs in products of microwave-assisted pyrolysis of woody biomass – Distribution among solid, liquid and gaseous phases and effects of material composition

Microwave-assisted pyrolysis (MAP) of lignocellulosic biomass is a technique that could potentially be used to produce and upgrade renewable energy carriers. However, there is no available information about the formation of dioxins and other organic pollutants in MAP treatment of woody biomass. In this study, MAP experiments were conducted in lab-scale using virgin softwood, bark, and impregnated wood as feedstocks. The non-condensable gas, liquid (fractionated into aqueous and oil phases), and char fractions generated during pyrolysis were collected and analysed for polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs). The concentrations of PCDDs, PCDFs and PCNs in the pyrolysis products ranged from 0.52 to 43.7 ng kg(-1). All investigated compound groups were most abundant in the oil fraction, accounting for up to 68% (w/w) of the total concentrations. The highest PCDD, PCDF and PCN concentrations were found from the pyrolysis of bark, which has relatively high contents of chlorine and mineral matter, followed by impregnated wood, which contains organic and metal-based preservatives. The homologue profiles of all three compound groups were dominated by the less chlorinated homologues. The homologue abundance decreased as the degree of chlorination increased. This trend was observed for all three feedstocks.

Mechanistic evaluation of polychlorinated dibenzo-p-dioxin, dibenzofuran and naphthalene isomer fingerprints in microwave pyrolysis of biomass

Isomer distribution patterns of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and naphthalenes (PCNs) were investigated in microwave-assisted pyrolysis (MAP) products of woody biomass. The feedstocks included bark and impregnated wood. The results indicated that isomer distributions in MAP are more selective compared to those reported from wood burning and waste incineration. Favored formation of 4-MoCDF and highly selective chlorine substitution at the 2,4-position observed during MAP suggested a preferred formation pathway of PCDFs involving (chloro)phenol precursors followed by subsequent chlorination. The PCDD distribution was dominated by isomers typically formed from chlorophenol condensation at relatively low temperature. The PCN isomer distributions showed a tendency for sequential chlorination from non-substituted naphthalene at successive positions. The presence of isomers such as 1-MoCDD, 4-MoCDF, 1,2,3-TriCN with low thermodynamic stability indicates that kinetic factors may be important in the MAP process.

CHAPTER 3:The Thermochemical Conversion of Biomass into High-Value Products: Microwave Pyrolysis

Thermochemical conversion of biomass appears to be one of the most promising methods by which the knowledge-based biobased economy will develop. With mankind’s insatiable hunger for electricity, chemicals, road transport fuels and aviation fuels showing no signs of abating we need drop-in replacements for coal and crude oil. Through application of microwave heating in place of conventional heating a greater level of control and tunability is possible. Furthermore, microwave processing of biomass offers lower temperatures than flash pyrolysis typically in the order of 200 °C in comparison with >400 °C that will have a significant impact on cost reduction and operational safety. Alternatively, microwave-assisted hydrothermal treatment of biomass offers a different product stream and is particularly effective for biomass with high water content such as food waste. This methodology generates predominately sugars instead of bio-oil, through depolymerisation of cellulose and hemicellulose generating fermentable sugars a wide range of chemicals and fuels can be produced by enzymatic routes.