Assessing economically viable carbon reductions for the production of ammonia from biomass gasification

Greenhouse gas emissions from fertiliser production are set to increase before stabilising due to the increasing demand to secure sustainable food supplies for a growing global population. However, avoiding the impacts of climate change requires all sectors to decarbonise by a very high level within several decades. Economically viable carbon reductions of substituting natural gas reforming with biomass gasification for ammonia production are assessed using techno-economic and life cycle assessment. Greenhouse gas savings of 65% are achieved for the biomass gasification system and the internal rate of return is 9.8% at base-line biomass feedstock and ammonia prices. Uncertainties in the assumptions have been tested by performing sensitivity analysis, which show, for example with a ±50% change in feedstock price, the rate of return ranges between -0.1% and 18%. It would achieve its target rate of return of 20% at a carbon price of £32/t CO, making it cost competitive compared to using biomass for heat or electricity. However, the ability to remain competitive to investors will depend on the volatility of ammonia prices, whereby a significant decrease would require high carbon prices to compensate. Moreover, since no such project has been constructed previously, there is high technology risk associated with capital investment. With limited incentives for industrial intensive energy users to reduce their greenhouse gas emissions, a sensible policy mechanism could target the support of commercial demonstration plants to help ensure this risk barrier is resolved. © 2013 The Authors.

New biomass derived carbon catalysts for biomass valorization

Due to diminishing petroleum reserves, unsteady market situation and the environmental concerns associated with utilization of fossil resources, the utilization of renewables for production of energy and chemicals (biorefining) has gained considerable attention. Biomass is the only sustainable source of organic compounds that has been proposed as petroleum equivalent for the production of fuels, chemicals and materials. In fact, it would not be wrong to say that the only viable answer to sustainably convene our future energy and material requirements remain with a bio-based economy with biomass based industries and products. This has prompted biomass valorization (biorefining) to become an important area of industrial research. While many disciplines of science are involved in the realization of this effort, catalysis and knowledge of chemical technology are considered to be particularly important to eventually render this dream to come true. Traditionally, the catalyst research for biomass conversion has been focused primarily on commercially available catalysts like zeolites, silica and various metals (Pt, Pd, Au, Ni) supported on zeolites, silica etc. Nevertheless, the main drawbacks of these catalysts are coupled with high material cost, low activity, limited reusability etc. – all facts that render them less attractive in industrial scale applications (poor activity for the price). Thus, there is a particular need to develop active, robust and cost efficient catalytic systems capable of converting complex biomass molecules. Saccharification, esterification, transesterification and acetylation are important chemical processes in the valorization chain of biomasses (and several biomass components) for production of platform chemicals, transportation fuels, food additives and materials. In the current work, various novel acidic carbons were synthesized from wastes generated from biodiesel and allied industries, and employed as catalysts in the aforementioned reactions. The structure and surface properties of the novel materials were investigated by XRD, XPS, elemental analysis, SEM, TEM, TPD and N2-physisorption techniques. The agro-industrial waste derived sulfonic acid functionalized novel carbons exhibit excellent catalytic activity in the aforementioned reactions and easily outperformed liquid H2SO4 and conventional solid acids (zeolites, ion-exchange resins etc). The experimental results indicated strong influence of catalyst pore-structure (pore size, pore-volume), concentration of –SO3H groups and surface properties in terms of the activity and selectivity of these catalysts. Here, a large pore catalyst with high –SO3H density exhibited the highest esterification and transesterification activity, and was successfully employed in biodiesel production from fatty acids and low grade acidic oils. Also, a catalyst decay model was proposed upon biodiesel production and could explain that the catalyst loses its activity mainly due to active site blocking by adsorption of impurities and by-products. The large pore sulfonated catalyst also exhibited good catalytic performance in the selective synthesis of triacetin via acetylation of glycerol with acetic anhydride and out-performed the best zeolite H-Y with respect to reusability. It also demonstrated equally good activity in acetylation of cellulose to soluble cellulose acetates, with the possibility to control cellulose acetate yield and quality (degree of substitution, DS) by a simple adjustment of reaction time and acetic anhydride concentration. In contrast, the small pore and highly functionalized catalysts obtained by hydrothermal method and from protein rich waste (Jatropha de-oiled waste cake, DOWC), were active and selective in the esterification of glycerol with fatty acids to monoglycerides and saccharification of cellulosic materials, respectively. The operational stability and reusability of the catalyst was found to depend on the stability of –SO3H function (leaching) as well as active site blocking due to adsorption of impurities during the reaction. Thus, our results corroborate the potential of DOWC derived sulfated mesoporous active carbons as efficient integrated solid acid catalysts for valorization of biomass to platform chemicals, biofuel, bio-additive, surfactants and celluloseesters.

Improved models for estimating temporal changes in carbon sequestration in above-ground biomass of mixed-species environmental plantings

Plantings of mixed native species (termed 'environmental plantings') are increasingly being established for carbon sequestration whilst providing additional environmental benefits such as biodiversity and water quality. In Australia, they are currently one of the most common forms of reforestation. Investment in establishing and maintaining such plantings relies on having a cost-effective modelling approach to providing unbiased estimates of biomass production and carbon sequestration rates. In Australia, the Full Carbon Accounting Model (FullCAM) is used for both national greenhouse gas accounting and project-scale sequestration activities. Prior to undertaking the work presented here, the FullCAM tree growth curve was not calibrated specifically for environmental plantings and generally under-estimated their biomass. Here we collected and analysed above-ground biomass data from 605 mixed-species environmental plantings, and tested the effects of several planting characteristics on growth rates. Plantings were then categorised based on significant differences in growth rates. Growth of plantings differed between temperate and tropical regions. Tropical plantings were relatively uniform in terms of planting methods and their growth was largely related to stand age, consistent with the un-calibrated growth curve. However, in temperate regions where plantings were more variable, key factors influencing growth were planting width, stand density and species-mix (proportion of individuals that were trees). These categories provided the basis for FullCAM calibration. Although the overall model efficiency was only 39-46%, there was nonetheless no significant bias when the model was applied to the various planting categories. Thus, modelled estimates of biomass accumulation will be reliable on average, but estimates at any particular location will be uncertain, with either under- or over-prediction possible. When compared with the un-calibrated yield curves, predictions using the new calibrations show that early growth is likely to be more rapid and total above-ground biomass may be higher for many plantings at maturity. This study has considerably improved understanding of the patterns of growth in different types of environmental plantings, and in modelling biomass accumulation in young (<25. years old) plantings. However, significant challenges remain to understand longer-term stand dynamics, particularly with temporal changes in stand density and species composition. © 2014.

Removal of paracetamol on biomass-derived activated carbon: Modeling the fixed bed breakthrough curves using batch adsorption experiments

The remediation of paracetamol (PA), an emerging contaminant frequently found in wastewater treatment plants, has been studied in the low concentration range (0.3–10 mg L−1) using as adsorbent a biomass-derived activated carbon. PA uptake of up to 100 mg g−1 over the activated carbon has been obtained, with the adsorption isotherms being fairly explained by the Langmuir model. The application of Reichemberg and the Vermeulen equations to the batch kinetics experiments allowed estimating homogeneous and heterogeneous diffusion coefficients, reflecting the dependence of diffusion with the surface coverage of PA. A series of rapid small-scale column tests were carried out to determine the breakthrough curves under different operational conditions (temperature, PA concentration, flow rate, bed length). The suitability of the proposed adsorbent for the remediation of PA in fixed-bed adsorption was proven by the high PA adsorption capacity along with the fast adsorption and the reduced height of the mass transfer zone of the columns. We have demonstrated that, thanks to the use of the heterogeneous diffusion coefficient, the proposed mathematical approach for the numerical solution to the mass balance of the column provides a reliable description of the breakthrough profiles and the design parameters, being much more accurate than models based in the classical linear driving force.

Implications of patterns of carbon pools and fluxes across a semiarid environmental gradient

Landscape scale environmental gradients present variable spatial patterns and ecological processes caused by climate, topography and soil characteristics and, as such, offer candidate sites to study environmental change. Data are presented on the spatial pattern of dominant species, biomass, and carbon pools and the temporal pattern of fluxes across a transitional zone shifting from Great Basin Desert scrub, up through pinyon-juniper woodlands and into ponderosa pine forest and the ecotones between each vegetation type. The mean annual temperature (MAT) difference across the gradient is approximately 3 degrees C from bottom to top (MAT 8.5-5.5) and annual precipitation averages from 320 to 530 mm/yr, respectively. The stems of the dominant woody vegetation approach a random spatial pattern across the entire gradient, while the canopy cover shows a clustered pattern. The size of the clusters increases with elevation according to available soil moisture which in turn affects available nutrient resources. The total density of woody species declines with increasing soil moisture along the gl-adient, but total biomass increases. Belowground carbon and nutrient pools change from a heterogenous to a homogenous distribution on either side of the woodlands. Although temperature controls the: seasonal patterns of carbon efflux from the soils, soil moisture appears to be the primary driving variable, but response differs underneath the different dominant species, Similarly, decomposition of dominant litter occurs faster-at the cooler and more moist sites, but differs within sites due to litter quality of the different species. The spatial pattern of these communities provides information on the direction of future changes, The ecological processes that we documented are not statistically different in the ecotones as compared to the: adjoining communities, but are different at sites above the woodland than those below the woodland. We speculate that an increase in MAT will have a major impact on C pools and C sequestering and release processes in these semiarid landscapes. However, the impact will be primarily related to moisture availability rather than direct effects of an increase in temperature. (C) 1998 Elsevier Science B.V.

Measuring and monitoring soil organic carbon stocks in agricultural lands for climate mitigation

Policies that encourage greenhouse-gas emitters to mitigate emissions through terrestrial carbon (C) offsets – C sequestration in soils or biomass – will promote practices that reduce erosion and build soil fertility, while fostering adaptation to climate change, agricultural development, and rehabilitation of degraded soils. However none of these benefits will be possible until changes in C stocks can be documented accurately and cost-effectively. This is particularly challenging when dealing with changes in soil organic C (SOC) stocks. Precise methods for measuring C in soil samples are well established, but spatial variability in the factors that determine SOC stocks makes it difficult to document change. Widespread interest in the benefits of SOC sequestration has brought this issue to the fore in the development of US and international climate policy. Here, we review the challenges to documenting changes in SOC stocks, how policy decisions influence offset documentation requirements, and the benefits and drawbacks of different sampling strategies and extrapolation methods.

Hydrothermal technologies for the production of fuels and chemicals from biomass

Biomass and non-food crop residues are seen as relatively low cost and abundant renewable sources capable of making a large contribution to the world’s future energy and chemicals supply. Signifi cant quantities of ethanol are currently produced from biomass via biochemical processes, but thermochemical conversion processes offer greater potential to utilize the entire biomass source to produce a range of products. This chapter will review thermochemical gasifi cation and pyrolysis methods with a focus on hydrothermal liquefaction processes. Hydrothermal liquefaction is the most energetically advantageous thermochemical biomass conversion process. If the target is to produce sustainable liquid fuels and chemicals and reduce the impact of global warming as a result of carbon dioxide, nitrous oxide, and methane emissions (i.e., protect the natural environment), the use of “green” solvents, biocatalysts and heterogeneous catalysts must be the main R&D initiatives. As the biocrude produced from hydrothermal liquefaction is a complex mixture which is relatively viscous, corrosive, and unstable to oxidation (due to the presence of water and oxygenated compounds), additional upgrading processes are required to produce suitable biofuels and chemicals.

The utilization of waste date seed as bio-oil and activated carbon by pyrolysis process

The renovation of biomass waste in the form of date seed waste into activated carbon and biofuel by fixed bed pyrolysis reactor has been focused in this study to obtain gaseous, liquid, and solid products. The date seed in particle form is pyrolysed in an externally heated fixed bed reactor with nitrogen as the carrier gas. The reactor is heated from 400◦C to 600◦C. A maximum liquid yield of 50wt.% and char of 30wt.% are obtained at a reactor bed temperature of 500◦C with a running time of 120 minutes. The oil is found to possess favorable flash point and reasonable density and viscosity. The higher calorific value is found to be 28.636 MJ/kg which is significantly higher than other biomass derived. Decolonization of 85–97% is recorded for the textile effluent and 75–90% for the tannery effluent, in all cases decreasing with temperature increase. Good adsorption capacity of the prepared activated carbon in case of diluted textile and tannery effluent was found.

Production of liquid fuel and activated carbon from mahogany seed by using pyrolysis technology

The renovation of biomass waste in the form of Mahogany seed waste into bio-fuel as well as activated carbon by fixed bed pyrolysis reactor has been taken into consideration in this study. The mahogany seed in particle form is pyrolyzed in an enormously heated fixed bed reactor with nitrogen as the carrier gas. The reactor is heated from 4000C to 6000C using a external heater in which rice husk and charcoal are used as the heater biomass fuel. Reactor bed temperature, running time and feed particle size have been varied to get the optimum operating conditions of the system. The parameters are found to influence the product yields to a large extent. A maximum liquid and char yield are 49 wt. % and 35 wt. % respectively obtained at a reactor bed temperature 5000C when the running time is 90 minutes. Acquired pyrolyzed oil at these optimal process conditions were analyzed for some of their properties as an alternative fuel. The oil possesses comparable flame temperature, favorable flash point and reasonable viscosity along with somewhat higher density. The kinematic viscosity of the derived fuel is 3.8 cSt and density is 1525 kg/m3. The higher calorific value is found 32.4 MJ/kg which is significantly higher than other biomass derived fuel. Moderate adsorption capacity of the prepared activated carbon in case of methyl blue & tea water was also revealed.

CO2 reforming of toluene as model compound of biomass tar on Ni/Palygorskite

Catalytic CO2 reforming of biomass tar on palygorskite-supported nickel catalysts using toluene as a model compound of biomass tar was investigated. The experiments were performed in a bench scale installation a fixed bed reactor. All experiments were carried out at 650, 750, 800 °C and atmospheric pressure. The effect of Ni loading, reaction temperature and concentration of CO2 on H2 yield and carbon deposit was investigated. Ni/Palygorskite (Ni/PG) catalysts with Ni/PG ratios of 0%, 2%, 5% and 8% were tested, the last two show the best performance. H2 yield and carbon deposit diminished with the increase of reaction temperature, Ni loading, and CO2 concentration.

Regional contingencies in the relationship between aboveground biomass and litter in the world’s grasslands

Based on regional-scale studies, aboveground production and litter decomposition are thought to positively covary, because they are driven by shared biotic and climatic factors. Until now we have been unable to test whether production and decomposition are generally coupled across climatically dissimilar regions, because we lacked replicated data collected within a single vegetation type across multiple regions, obfuscating the drivers and generality of the association between production and decomposition. Furthermore, our understanding of the relationships between production and decomposition rests heavily on separate meta-analyses of each response, because no studies have simultaneously measured production and the accumulation or decomposition of litter using consistent methods at globally relevant scales. Here, we use a multi-country grassland dataset collected using a standardized protocol to show that live plant biomass (an estimate of aboveground net primary production) and litter disappearance (represented by mass loss of aboveground litter) do not strongly covary. Live biomass and litter disappearance varied at different spatial scales. There was substantial variation in live biomass among continents, sites and plots whereas among continent differences accounted for most of the variation in litter disappearance rates. Although there were strong associations among aboveground biomass, litter disappearance and climatic factors in some regions (e.g. U.S. Great Plains), these relationships were inconsistent within and among the regions represented by this study. These results highlight the importance of replication among regions and continents when characterizing the correlations between ecosystem processes and interpreting their global-scale implications for carbon flux. We must exercise caution in parameterizing litter decomposition and aboveground production in future regional and global carbon models as their relationship is complex.