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AbstractCalcium oxide supported on ZrO2 is a highly active catalyst for base‐catalyzed reactions such as aldol‐type reactions and transesterification reactions. The role of key parameters during preparation, that is, impregnation versus precipitation, heat treatment, and metal oxide loading on the basicity and catalytic activity were investigated for CaO supported on ZrO2. An impregnation of 10 wt % CaO on monoclinic zirconia followed by heat treatment at 600 °C resulted in high activity for the self‐condensation reaction of acetone. An evaluation of a series of CaO/ZrO2 samples with different loadings showed that the activity increased for impregnated amounts per gram catalyst of 0–10 wt % CaO, and at higher loading the activity decreased as a result of a decrease in dispersion. The number of strong base sites (calculated from CO2 desorbed at temperatures higher than 625 °C) correlated with the activity. For MgO, CaO, SrO, and BaO on zirconia the catalytic activity increased as the ionic radius of the metal cation increased, suggesting the impact of base strength on catalytic performance.

AbstractTransition to a bio‐based economy will create new demand for biomass, e.g. the increasing use of bioenergy, but the impacts on existing markets are unclear. Furthermore, there is a growing public concern on the sustainability of biomass. This study proposes a methodological framework for mapping national biomass flows based on domestic production‐consumption and cross‐border trade, and respective share of sustainably‐certified biomass. A case study was performed on the Netherlands for 2010‐2011, focusing on three categories: (i) woody biomass, (ii) oils and fats, and (iii) carbohydrates. Between 2010‐2011 few major shifts were found, besides the increasing biofuel production. The share of sustainably‐certified feedstock is growing in many categories. Woody biomass used for energy amounted to 3.45 MT, including 1.3 MT imported wood pellets ( >85% certified). About 0.6 MT of oils and fats and 1.2 MT (estimation) of carbohydrates were used for biofuel production. It is assumed that only certified materials were used for biofuel production. For non‐energy purpose, more than 50% of woody biomass used was either certified or derived from recycled streams. Certified oils has entered the Dutch food sector since 2011, accounted for 7% of total vegetable oils consumption. It is expected that carbohydrates will also be certified in the near future. Methodological challenges encountered are: inconsistency in data definitions, lack of coherent cross‐sectorial reporting systems, low reliability of bilateral trade statistics, lack of transparency in biomass supply chains, and disparity in sustainability requirements. The methodology may be expanded for future projection in different scenarios. © 2013 Society of Chemical Industry and John Wiley & Sons, Ltd

Extreme summer droughts are expected to occur more often in the future in NW Europe due to climate change. These droughts might accelerate the rate of peat oxidation in drained peat areas, with impacts on soil subsidence, GHG emission and water quality. This study aimed at providing more insight in the oxidation of deep peat layers that had not previously been exposed to air, the so-called secondary decomposition. We incubated two types of peat (eutrophic and oligotrophic), sampled from permanently anoxic peat layers from nature reserves and agricultural peat meadows. Peat samples were incubated for thirteen weeks under anoxic conditions, but were exposed to air for one to eight weeks. The production of CO2 and CH4 was quantified as a proxy for decomposition; concentrations of soluble nutrients and phenolic compounds were also measured. The results showed that oxygenation led to a steep increase in the rate of decomposition, indicated by higher carbon loss rates during and after oxygenation compared to non-oxygenated samples. Carbon loss rates increased more for eutrophic peat (agricultural area: 352%, nature reserve: 182%) than for oligotrophic peat (83% and 159% respectively). Most peat samples investigated showed higher post-oxygenation CO2 and/or CH4 production compared to the anoxic pre-oxygenation period. This indicates that oxygenation stimulates decomposition, even after anoxic conditions have returned. Contrary to the enzymic latch theory, no effects of oxygenation on the concentrations of soluble or condensed phenolic compounds were detected. Soluble nutrient concentrations did not change due to oxygenation either. Noteworthy is the occurrence of pyrite mineralization and associated acidification in eutrophic peat. Thus, low summer water levels, for example due to climate change, should be avoided in order to limit exceptionally high decomposition rates and associated problems such as increasing subsidence rates, greenhouse gas emission, sulfate release and acidification.

The aim of this study was to analyze whether, and if so, in what way risks would influence the design,costs and routing of CO2pipelines. This article assesses locational and societal risks of CO2pipelinetransport and analyses whether rerouting or implementing additional risk mitigation measures is themost cost-effective option. The models EFFECTS and RISKCURVES are used to estimate the dispersion andrisk, respectively. The pipeline routes are optimized by using the least cost path function in ArcGIS.This article evaluates three case studies in the Netherlands. The results show that pipelines transportingdense phase CO2(8–17 MPa) with a minimal amount of risk mitigation measures already meet the 10−6locational risk required in the Netherlands. 10−6locational risks of 135 m are calculated for intermediatepumping stations, handling 450 kg CO2/s (about 14 Mt CO2/year). In all the cases, pumping stations couldbe located along the pipeline route without any problem.For the cases studied transporting gaseous CO2(1.5–3 MPa) leads to larger 10−6locational risk distancesthan transporting dense phase CO2. This is caused by the large momentum behind a dense phase CO2release, leading to smaller but higher jet and to a higher mixing rate with the surrounding air than for agaseous CO2release.Based on our analysis, it can be concluded that dense phase CO2transport is safe if it is well organized.The risks are manageable and widely accepted under current legislation. In addition, risk mitigationmeasures, like marker tape and increased surveillance, are available which reduce the risk significantlyand increase the costs only slightly. Pipeline routing for gaseous CO2transport appears more challengingin densely populated areas, because larger safety zones are attached to it.

This paper analyzes the ability of water utilities to contribute to sustainability transition processes. More specifically, we compare the capacity of utilities, embedded in purely public, mixed and largely private governance modes, to innovate. We employ dynamic capabilities as core indicators for innovativeness and therefore as major enabling factors for sustainable sector transitions. We assess the relationship between governance modes and innovation by conducting an in-depth comparative analysis of three water utilities, each within a differing governance mode along the public-to-private continuum: Zurich, Berlin and Leeds. While we find that the private and mixed governance modes have an increased degree of innovativeness, they perform lower in terms of static sustainability criteria than the public mode. We therefore conclude that the impact of privatization on sustainability transitions in the water sector involves multi-dimensional trade-offs between static and dynamic sustainability criteria.

Some Parties (Countries) to the UNFCCC decided to include the carbon uptake by harvested wood products (HWP) in a new general accounting framework after 2012 (post Kyoto). The analysis aims to make a comparison between the cascaded use of HWP and the use of wood for energy. We combine the new HWP framework with an assumed increased 50 million m3harvest level in Canada and evaluate the impact of the GHG emissions over a 100-year period. Our reference case assumes all harvested wood is an immediate CO2emission (IPCC default) and no substitution effects, i.e. annual GHG emissions of 41 million tonnes CO2eq. In our wood utilization scenario's, harvested trees are allocated (in varying shares) to three end-products: construction wood, paper products and pellets for power production. In comparison with our base case, a combination of fossil fuel substitution, material substitution and temporary carbon uptake by HWP leads to significant decreases in GHG emissions. All scenario's show annual GHG emission between 18 and 21 million tonnes CO2eqexcept for triple use without recycling (at least 24 million tonnes CO2eq). We conclude that GHG emissions of our scenarios are substantially lower than IPCC default. However, it is difficult to incorporate one single method to account for GHG uptake and emissions by HWP, due to end use efficiency and recycling options. Further GHG allocation over individual countries is not straightforward and needs further research. © 2013 Elsevier Ltd.

AbstractThe development of new and improved processes for the synthesis of bio‐based chemicals is one of the scientific challenges of our time. These new discoveries are not only important from an environmental point of view, but also represent an important economic opportunity, provided that the developed processes are selective and efficient. Bioethanol is currently produced from renewable resources in large amounts and, in addition to its use as biofuel, holds considerable promise as a building block for the chemical industry. Indeed, further improvements in production, both in terms of efficiency and feedstock selection, will guarantee availability at competitive prices. The conversion of bioethanol into commodity chemicals, in particular direct ‘drop‐in’ replacements is, therefore, becoming increasingly attractive, provided that the appropriate (catalytic) technology is in place. The production of green and renewable 1,3‐butadiene is a clear example of this approach. The Lebedev process for the one‐step catalytic conversion of ethanol to butadiene has been known since the 1930s and has been applied on an industrial scale to produce synthetic rubber. Later, the availability of low‐cost oil made it more convenient to obtain butadiene from petrochemical sources. The desire to produce bulk chemicals in a sustainable way and the availability of low‐cost bioethanol in large volumes has, however, resulted in a renaissance of this old butadiene production process. This paper reviews the catalytic aspects associated with the synthesis of butadiene via the Lebedev process, as well as the production of other, mechanistically related bulk chemicals that can be obtained from (bio)ethanol.