of various technologies, recommendations are made on further research on the appropriate low cost technologies, especially using solid waste as low cost materials for biogas purification and upgrading.
The best catalysts for promoting char gasification are Group I metals, particularly lithium and potassium, although other metals are active to a lesser extent. The most prevalent metal naturally in biomass char is potassium, which is not only inherently active, but volatilises to become finely distributed throughout the char mass. The formation of an active carbon/potassium complex is frequently proposed. Calcium is the other most common active metal found in biomass, but is far less effective and less volatile. In a gasification system the metals remain as carbonate due to the action of carbon dioxide. The alkali metals can react with silica to form silicates, which prevents catalytic action. Transition metals can also participate in catalysis of gasification; iron accelerates gasification and nickel prevents carbon deposition, which helps in conditioning biomass-derived syngas. Volatile iron pentacarbonyl has been identified as a promoter of the char gasification step, with catalytic activity related to the finely dispersed low-valency metal atoms generated during the thermo-decomposition of biomass.
The literature on the presence of heavy metals in contaminated wastes is reviewed. Various categories of materials produced from domestic and industrial activities are included, but municipal solid waste, which is a more complex material, is excluded. This review considers among the most abundant the following materials - wood waste including demolition wood, phytoremediation scavengers and chromated copper arsenate (CCA) timber, sludges including de-inking sludge and sewage sludge, chicken litter and spent pot liner. The partitioning of the metals in the ashes after combustion or gasification follows conventional behaviour, with most metals retained, and higher concentrations in the finer sizes due to vaporisation and recondensation. The alkali metals have been shown to catalyse the biomass conversion, particularly lithium and potassium, although other metals are active to a lesser extent. The most prevalent in biomass is potassium, which is not only inherently active, but volatilises to become finely distributed throughout the char mass. Because the metals are predominantly found in the ash, the effectiveness of their removal depends on the efficiency of the collection of particulates. The potential for disposal into soil depends on the initial concentration in the feed material.
This research investigates the catalytic properties of char which was recovered directly from a biomass gasifier. Poplar wood was gasified in steam and CO 2 environments in a fluidized bed reactor at temperatures ranging from 550 to 920°C. Char was composed of 85% carbon with concentrations of N, H, and S between 0.3% and 3%, depending on gasification conditions. The inorganics (Ca, K, Na, P, Si, Mg) were quantified, revealing that Ca was present in the highest concentration (0.5-1%), followed by K, ranging from 0.1% to 0.8%. The char had catalytic activity for decomposition of methane, which was used as a model molecule. The quantity of inorganics in the char was modified by acid washing in 16% aqueous HCl, which removed >95% of Ca, K, P, and Mg from the char. This resulted in an 18% decrease in the quantity of methane reacted compared to the original char sample, demonstrating that inorganics, which only make up approximately 2% of the char, play a significant role in its catalytic activity for methane cracking reactions. In addition, carbon was found to play an important role in the catalytic activity of the char, both as a catalyst and a support on which the inorganics were dispersed. The activity of carbon free ash was approximately 90% lower than that of char, and deactivated to have no measurable activity after 45 min on stream, demonstrating the importance of carbon and dispersed inorganics for catalytic activity. When char was heated to 1000°C in N 2 , inorganics and oxygen migrated to the surface of the char, covering the carbon surface in a metal oxide layer. This decreased the catalytic activity by approximately 40%. Acidic (e.g. carboxylic, lactones) and basic (e.g. carbonyl, pyrone) oxygen functional groups were identified on the char surface. However, acidic oxygen groups desorbed at reaction temperatures, so these groups likely do not participate in cracking reactions.
Gasification provides a mechanism to convert solids, such as biomass, coal, or waste, into fuels that can be easily integrated into current infrastructure. This paper discusses the use of residual char from a biomass gasifier as a catalyst for tar decomposition and presents an investigation of the catalytic properties of the char. Poplar wood was gasified in a fluidized bed reactor at temperatures ranging from 550 to 920°C in reaction environments of 90% steam/10% N 2 and 90% N 2 /10% CO 2 . The properties of the char recovered from the process were analyzed, and the catalytic performance for hydrocarbon cracking reactions was tested. Brunauer−Emmett−Teller (BET) measurements showed that the surface area of the char was higher than conventional catalyst carriers. The surface area, which ranged from 429 to 687 m 2 g −1 , increased with temperature and reaction time. The catalytic activity of the char was demonstrated through testing the catalytic decomposition of methane and propane to produce H 2 and solid carbon. Higher char surface area resulted in increased performance, but pore size distribution also affected the activity of the catalyst, and evidence of diffusion limitations in microporous char was observed. Clusters of iron were present on the surface of the char. After being used for catalytic applications, carbon deposition was observed on the iron cluster and on the pores of the char, indicating that these sites may influence the reaction. When the char was heated to 800°C in an inert (N 2 ), atmosphere mass loss was observed, which varied based on the type of char and the time. ESEM/EDX showed that when char was heated to 1000°C under N 2 , oxygen and metals migrated to the surface of the char, which may impact its catalytic activity. Through investigating the properties and performance of biomass gasification char, this paper demonstrates its potential to replace expensive tar decomposition catalysts with char catalysts, which are continuously produced on-site in the gasification process.
A B S T R A C TPyrolysis chars from wastes were investigated as sorbents for H 2 S removal from syngas. The H 2 S removal tests were performed at ambient temperature in various dry gas matrices (N 2 , Air, Syngas) to study the effect of the gas composition on the adsorption efficiency. Two chars were produced by the pyrolysis of: used wood pallets (UWP), and a 50/50% mixture of food waste (FW) and coagulation-flocculation sludge (CFS). The chars were functionalized by low-cost processes without chemicals: gas phase oxygenation and steam activation. Activated chars were the most efficient materials due to their large specific surface area, alkaline pH, basic O-containing groups and structural defects in graphene-like sheets. Raman analysis evidenced that inherent mineral species (especially Ca and Fe) increased the H 2 S removal efficiency by promoting the formation of metal sulfide and metal sulphate species at the char surface. Mesopores lower than 70 Å were revealed to be important adsorption sites. Under dry Syngas matrix, the chars remained efficient and selective toward H 2 S removal despite the presence of CO 2 , while O 2 in the Air matrix decreased their removal capacity due to the formation of sulfur acid species. The most efficient material was the steam activated char from FW/CFS, with a removal capacity of 65 mg H2S .g −1 under dry syngas. This char was proved to be completely regenerated with a thermal treatment under N 2 at 750°C. This study demonstrated that activated chars from food waste and sludge could be used as eco-friendly, affordable, and selective materials for syngas desulfurization even under dry atmosphere.
The behaviour of non-stoichiometric hydroxyapatite (HA) during the calcination in a solid bed was investigated. The structural properties are described in terms of the specific surface area. Calcination led to a significant decrease of the specific surface area by particle coalescence and densification. Hydroxyapatite begins to shrink near 780 • C and reaches 97% theoretical density at 1100 • C. The specific surface area and density variations are caused both by sintering and chemical reaction. Sintering data from these solids were correlated as a function of time and temperature. The rate of sintering is assumed to obey an Arrhenius equation. These results are compared with a number of literature models describing the mechanism of sintering kinetics using the specific surface area, and a good agreement is observed. The kinetic equation used is based on sintering driven by the curvature gradient in the interparticle neck region associated with initial stage sintering. Then, the decline in specific surface area is accurately described by the empirical equation of the form dS/dt = −B(T)k b. The changing value of b, also known as the "order" of the reaction, suggests that the diffusion mechanism for loss of surface area may be a function of the temperature.
Heavy metal pollution is a major environmental concern because of the toxicity to humans and plants. This toxicity is lethal even in trace quantities and metals have a great tendency to bioaccumulate. The efficiency of phosphate and apatites M 10 (PO 4 ) 6 (OH) 2 , M: Metal, in particular, in removing and immobilizing heavy metals from wastewater, groundwater (as permeable reactive barriers for in situ site remediation), fly ash, dredged sludges and contaminated soil has led to various studies to understand and explain the mechanisms involved. This paper will address the use of apatite as sorbent and stabilizing agents for the removal of heavy metals from various media. Efficient physico-chemical immobilization of heavy metals brings new perspectives for reuse of polluted waste water, soils and land treated by selected phosphates.
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