Pyrolysis of waste tyres: A review

Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H₂, C₁–C₄ hydrocarbons, CO₂, CO and H₂S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.     

An experimental study on fermentative H2 production from food waste as affected by pH

Batch dark fermentation experiments were performed on food waste and mixtures of food waste and wastewater activated sludge to evaluate the influence of pH on biological H₂ production and compare the process performance with and without inoculum addition. The effect of a preliminary thermal shock treatment of the inoculum was also investigated as a means to harvest the hydrogenogenic biomass. The best performance in terms of both H₂ generation potential and process kinetics was observed at pH = 6.5 under all experimental conditions (no inoculum, and untreated or thermally treated inoculum added). H₂ production from food waste was found to be feasible even without inoculum addition, although thermal pre-treatment of the inoculum notably increased the maximum production and reduced the lag phase duration. The analysis of the fermentation products indicated that the biological hydrogen production could be mainly ascribed to a mixed acetate/butyrate-type fermentation. However, the presence of additional metabolites in the digestate, including propionate and ethanol, also indicated that other metabolic pathways were active during the process, reducing substrate conversion into hydrogen. The plateau in H₂ generation was found to mirror the condition at which soluble carbohydrates were depleted. Beyond this condition, homoacetogenesis probably started to play a role in the degradation process.     

The development of low cost adsorbents from clay and waste materials: a review

Increased energy consumption due to industrial growth has increased the levels of carbon dioxide (CO₂) emission being released into the atmosphere. CO₂ emission is a type of greenhouse gas which is a major cause of global warming. Since the issue of CO₂ emissions has drawn much attention in recent years, the development of CO₂ capture technology has become a necessity. Although CO₂ adsorbents are still at the early development stage, it has been suggested that CO₂ adsorbents are the most effective technology in controlling CO₂ emissions. Solid adsorbents have great potential as an alternative method to conventional adsorbents in adsorbing CO₂. In this paper, low cost adsorbents including activated carbon, zeolites, mesoporous silica and clays are discussed in terms of adsorbent preparation methods and CO₂ adsorption capacity. The low cost adsorbents are mainly derived from waste materials such as fly ash, steel slag, red mud, bagasses wastes and wood wastes. Besides that, natural resources such as clays have also been applied as low cost CO₂ adsorbents. Surface modifications have also been applied to the low cost adsorbents, including metal ion exchange and amine impregnation to enhance CO₂ adsorption capacity. In the last section, the current status of CO₂ adsorbents is summarized and future trends are discussed briefly to predict the potential materials which can be applied as CO₂ adsorbents.     

Removal of H2S using molten carbonate at high temperature

Gasification is considered to be an effective process for energy conversion from various sources such as coal, biomass, and waste. Cleanup of the hot syngas produced by such a process may improve the thermal efficiency of the overall gasification system. Therefore, the cleanup of hot syngas from biomass gasification using molten carbonate is investigated in bench-scale tests. Molten carbonate acts as an absorbent during desulfurization and dechlorination and as a thermal catalyst for tar cracking. In this study, the performance of molten carbonate for removing H₂S was evaluated. The temperature of the molten carbonate was set within the range from 800 to 1000 °C. It is found that the removal of H₂S is significantly affected by the concentration of CO₂ in the syngas. When only a small percentage of CO₂ is present, desulfurization using molten carbonate is inadequate. However, when carbon elements, such as char and tar, are continuously supplied, H₂S removal can be maintained at a high level.To confirm the performance of the molten carbonate gas-cleaning system, purified biogas was used as a fuel in power generation tests with a molten carbonate fuel cell (MCFC). The fuel cell is a high-performance sensor for detecting gaseous impurities. When purified gas from a gas-cleaning reactor was continuously supplied to the fuel cell, the cell voltage remained stable. Thus, the molten carbonate gas-cleaning reactor was found to afford good gas-cleaning performance.     

Aerobic biometer analysis of glucose and starch biodegradation

The ASTM D5210-91 protocol for evaluating the biodegradability of a polymer was examined. The reactor design was modified not only to account for the total CO₂ evolved but also to allow for the simultaneous carbon assessment in microbes, soluble products, and solid samples. Improvements in the test procedure were implemented such as (1) refining the CO₂ pretrap and posttrap design, (2) optimizing the carbon dioxide removal efficiency, (3) accounting for the total polymeric carbon, (4) standardizing the inoculum, and (5) revising the nutrient medium. By growing the sludge on a suitable substrate prior to polymeric exposure, a constant microbial density was obtained. The modified ASTM method provides an assessment of the polymeric carbon degradation at any given time. The results of this work have specific significance to the behavior of polymers in a sewage waste treatment plant, where sludge is continuously being acrated, and also for aerobic biodegradation in general.     

Development and calibration of a model for biohydrogen production from organic waste

Existing models for H₂ production are capable of predicting digester failure caused by a specific disturbance. However, they are based on studies using simple sugars, while it is known that H₂ production and fermentation kinetics vary with the composition and characteristics of the substrate used. Because the behaviour of biological processes may differ significantly when the digesting material is a complex matrix, such as organic waste, the aim of this study was to develop and calibrate a mathematical model for the prediction of hydrogen production on the basis of the results obtained from a laboratory scale experimental study using source-selected organic waste. The calibration was carried out for the most important kinetic parameters in mesophilic anaerobic digestion processes and also served as a sensitivity analysis for the influence of both the specific growth rate (μ_max and the half velocity constant (k_s), both of which are strongly dependant on the substrate used. High values of μ_max led to a shorter lag-time and to an overestimate of the cumulative final H₂ production relative to the experimentally measured production. Additionally, high values of k_s associated with amino acid and sugar fermentation corresponded to a lower rate of substrate consumption and to a greater lag-time for growth of hydrogen-producing microorganisms. In this case, a lower final H₂ production was predicted than that which was experimentally observed. Because the model development and calibration provided useful information concerning the role of the kinetic constants in the analysis of a fermentative H₂ production process from organic wastes, they may also represent a good foundation for the analysis of fermentative H₂ production from organic waste for pilot and full-scale applications.     

Anaerobic biodegradation of cellulosic material: Batch experiments and modelling based on isotopic data and focusing on aceticlastic and non-aceticlastic methanogenesis

Utilizing stable carbon isotope data to account for aceticlastic and non-aceticlastic pathways of methane generation, a model was created to describe laboratory batch anaerobic decomposition of cellulosic materials (office paper and cardboard). The total organic and inorganic carbon concentrations, methane production volume, and methane and CO₂ partial pressure values were used for the model calibration and validation. According to the fluorescent in situ hybridization observations, three groups of methanogens including strictly hydrogenotrophic methanogens, strictly aceticlastic methanogens (Methanosaeta sp.) and Methanosarcina sp., consuming both acetate and H₂/H₂CO₃ as well as acetate-oxidizing syntrophs, were considered. It was shown that temporary inhibition of aceticlastic methanogens by non-ionized volatile fatty acids or acidic pH was responsible for two-step methane production from office paper at 35 °C where during the first and second steps methane was generated mostly from H₂/H₂CO₃ and acetate, respectively. Water saturated and unsaturated cases were tested. According to the model, at the intermediate moisture (150%), much lower methane production occurred because of full-time inhibition of aceticlastic methanogens. At the lowest moisture, methane production was very low because most likely hydrolysis was seriously inhibited. Simulations showed that during cardboard and office paper biodegradation at 55 °C, non-aceticlastic syntrophic oxidation by acetate-oxidizing syntrophs and hydrogenotrophic methanogens were the dominant methanogenic pathways.     

Siloxanes removal from biogas by high surface area adsorbents

Biogas utilized for energy production needs to be free from organic silicon compounds, as their burning has damaging effects on turbines and engines; organic silicon compounds in the form of siloxanes can be found in biogas produced from urban wastes, due to their massive industrial use in synthetic product, such as cosmetics, detergents and paints.Siloxanes removal from biogas can be carried out by various methods (Mona, 2009, Ajhar et al., 2010, Schweigkofler and Niessner, 2001); aim of the present work is to find a single practical and economic way to drastically and simultaneously reduce both the hydrogen sulphide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleone et al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing the most volatile siloxane (hexamethyldisiloxane or L2) in a nitrogen stream, typically 100–200 ppm L2 over N₂, through an activated carbon powder bed; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best activated carbon shows an adsorption capacity of 0.1 g L2 per gram of carbon. The next thermogravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on L2 concentration. A regenerative carbon process is then carried out by heating the carbon bed up to 200 °C and flushing out the adsorbed L2 samples in a nitrogen stream in a three step heating procedure up to 200 °C. The adsorption capacity is observed to degrade after cycling the samples through several adsorption–desorption cycles.     

Long-term thermophilic mono-digestion of rendering wastes and co-digestion with potato pulp

In this study, mono-digestion of rendering wastes and co-digestion of rendering wastes with potato pulp were studied for the first time in continuous stirred tank reactor (CSTR) experiments at 55 °C. Rendering wastes have high protein and lipid contents and are considered good substrates for methane production. However, accumulation of digestion intermediate products viz., volatile fatty acids (VFAs), long chain fatty acids (LCFAs) and ammonia nitrogen (NH₄-N and/or free NH₃) can cause process imbalance during the digestion. Mono-digestion of rendering wastes at an organic loading rate (OLR) of 1.5 kg volatile solids (VS)/m³ d and hydraulic retention time (HRT) of 50 d was unstable and resulted in methane yields of 450 dm³/kg VS_fed. On the other hand, co-digestion of rendering wastes with potato pulp (60% wet weight, WW) at the same OLR and HRT improved the process stability and increased methane yields (500–680 dm³/kg VS_fed). Thus, it can be concluded that co-digestion of rendering wastes with potato pulp could improve the process stability and methane yields from these difficult to treat industrial waste materials.     

Co-gasification of wood and polyethylene with the aim of CO and H2 production

This article describes the gasification of polyethylene–wood mixtures to form syngas (H₂ and CO) with the aim of feedstock recycling via direct fermentation of syngas to ethanol. The aim was to determine the effects of four process parameters on process properties that give insight into the efficiency of gasification in general, and particularly into the optimum gasification conditions for the production of ethanol by fermentation of producer gas. Gasification experiments (fluidized bed, 800°–950°C) were done under different conditions to optimize the composition of syngas suitable for fermentation purposes. The data obtained were used for statistical analysis and modeling. In this way, the effect of each parameter on the process properties was determined and the model was used to predict the optimum gasification conditions. The parameters varied during the experiment were gasification temperature, equivalence ratio, the ratio of plastic to wood in the feed, and the amount of steam added to the process. The response models obtained proved to be statistically significant in the experimental domain. The optimum gasification conditions for maximization of carbon monoxide and hydrogen production were identified. The conditions are: temperature 900°C, equivalence ratio 0.15, amount of plastic in the feed 0.11 g/g feed, and amount of steam added 0.42 g/g feed. These optimum conditions are at the edge of the present experimental domain. The maximum combined CO and H₂ efficiency was 42%, and for the maximum yield of CO and H₂ it is necessary to minimize the polyethylene content, minimize the added steam and the equivalence ratio, and maximize temperature.     

Revisiting the elemental composition and the calorific value of the organic fraction of municipal solid wastes

In this work, the elemental content (C, N, H, S, O), the organic matter content and the calorific value of various organic components that are commonly found in the municipal solid waste stream were measured. The objective of this work was to develop an empirical equation to describe the calorific value of the organic fraction of municipal solid waste as a function of its elemental composition. The MSW components were grouped into paper wastes, food wastes, yard wastes and plastics. Sample sizes ranged from 0.2 to 0.5 kg. In addition to the above individual components, commingled municipal solid wastes were sampled from a bio-drying facility located in Crete (sample sizes ranged from 8 to 15 kg) and were analyzed for the same parameters. Based on the results of this work, an improved empirical model was developed that revealed that carbon, hydrogen and oxygen were the only statistically significant predictors of calorific value. Total organic carbon was statistically similar to total carbon for most materials in this work. The carbon to organic matter ratio of 26 municipal solid waste substrates and of 18 organic composts varied from 0.40 to 0.99. An approximate chemical empirical formula calculated for the organic fraction of commingled municipal solid wastes was C₃₂NH₅₅O₁₆.     

High rate mesophilic, thermophilic, and temperature phased anaerobic digestion of waste activated sludge: a pilot scale study

The paper reports the findings of a two-year pilot scale experimental trial for the mesophilic (35°C), thermophilic (55°C) and temperature phased (65+55°C) anaerobic digestion of waste activated sludge. During the mesophilic and thermophilic runs, the reactor operated at an organic loading rate of 2.2 kgVS/m(3)d and a hydraulic retention time of 20 days. In the temperature phased run, the first reactor operated at an organic loading rate of 15 kgVS/m(3)d and a hydraulic retention time of 2 days while the second reactor operated at an organic loading rate of 2.2 kgVS/m(3)d and a hydraulic retention time of 18 days (20 days for the whole temperature phased system). The performance of the reactor improved with increases in temperature. The COD removal increased from 35% in mesophilic conditions, to 45% in thermophilic conditions, and 55% in the two stage temperature phased system. As a consequence, the specific biogas production increased from 0.33 to 0.45 and to 0.49 m(3)/kgVS(fed) at 35, 55, and 65+55°C, respectively. The extreme thermophilic reactor working at 65°C showed a high hydrolytic capability and a specific yield of 0.33 g COD (soluble) per gVS(fed). The effluent of the extreme thermophilic reactor showed an average concentration of soluble COD and volatile fatty acids of 20 and 9 g/l, respectively. Acetic and propionic acids were the main compounds found in the acids mixture. Because of the improved digestion efficiency, organic nitrogen and phosphorus were solubilised in the bulk. Their concentration, however, did not increase as expected because of the formation of salts of hydroxyapatite and struvite inside the reactor.     

A Global Outlook to the Carbon Dioxide Emissions in the World and Emission Factors of the Thermal Power Plants in Turkey

World primary energy demand increases with increases in population and economic development. Within the last 25 yr, the total energy consumption has almost doubled. For the purpose of meeting this demand, fossil energy sources are used and various pollutants are generated. CO₂ is also one of these gases, which cannot be removed like other pollutants, and it causes greenhouse effect and climate change. Reducing the CO₂ emission is very important because of the environmental concerns and regulations, especially the Kyoto Protocol. This paper reviews the estimated world carbon emissions, Turkey's situation in electrical energy production, emission amounts estimated until the year 2020 and emission factors for dust, SO₂, NO_x and CO₂. The estimated results show that CO₂ emissions from thermal power plants in Turkey will make about 0.66 % of the global CO₂ emissions in 2020.     

Groundwater treatment and aquatic toxicity reduction at a chemical production site

Contaminated groundwater at a chemical antioxidant and phenolic resin chemical production site was subjected to treatability studies to develop design criteria for surface water discharge. Raw groundwater required pretreatment for total suspended solids (TSS) and color removal prior to treatment by ultraviolet light/hydrogen peroxide (UV/H₂O₂). Because of high capital and operating costs for UV/H₂O₂, biological treatment was evaluated as an alternate. Respirometric analyses showed that completely mixed activated sludge could be applied as a treatment technology to the groundwater. Biotreatment resulted in an approximately 70 percent reduction in soluble chemical oxygen demand (SCOD). Residual SCOD was recalcitrant to further biodegradation. The treated effluent was tested for aquatic toxicity using fathead minnows (Pimephales promelas) and Ceriodaphnia dubia and was found to be toxic. Toxicity reduction of biotreatment effluent was evaluated in bench-scale experiments using activated carbon adsorption, filtration, and UV/H₂O₂. Subsequent toxicity testing showed that filtration alone could reduce the bioeffluent toxicity and that residual SCOD was not the primary source of toxicity.     

有机固体废物生物法制氢的研究进展

综述了利用有机固体废物生物法制氢的原理和研究现状。城市有机固体废物、农业有机废物、工业有机废物是生物法制氢的主要原料。暗发酵制氢是利用有机废物厌氧消化的产酸阶段而产氢，pH、温度、水力停留时间、氢气分压、原料性质、微量元素含量、产甲烷微生物抑制剂等均影响氢气产率。光发酵制氢是利用光合厌氧细菌将挥发性有机酸转化为氢气和二氧化碳。暗发酵和光发酵制氢时，生物固定化有利于高速连续产氢。在有机废物处理和生物法制氢方面，暗发酵一光发酵、暗发酵一微生物燃料电池的组合工艺是具有前景的技术。今后的研究方向是原料的预处理技术、选育高效产氢菌株、发明高效反应器、优化处理工艺和处理条件等。     

In-situ bioremediation of hanford groundwater

The U.S. Department of Energy has generated liquid wastes containing radioactive and hazardous chemicals throughout the more than forty years of operation at its Hanford site in Washington State. Many of the waste components, including nitrate and carbon tetrachloride (CCl₄), have been detected in the Hanford groundwater. In-situ bioremediation of CCl₄ and nitrate is being considered to clean the aquifer. Preliminary estimates indicate that this technology should cost significantly less than ex-situ bioremediation and about the same as air stripping/granular activated carbon. In-situ bioremediation has the advantage of providing ultimate destruction of the contaminant and requires significantly less remediation time. Currently, a test site is under development. A computer-aided design tool is being used to design optimal remediation conditions by linking subsurface transport predictions, site characterization data, and microbial growth and contaminant destruction kinetics.     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Removal of Reactive Blue 19 dye from synthetic wastewater using UV/H2O2 and UV/Cl advanced oxidation processes

The textile and dyeing industries are among the largest water-consuming and polluting industries in the world. The most important feature of the textile dyeing industry wastewater is its color, due to the use of colored materials. Most of these dye compounds are resistant to conventional purification methods and their biodegradation is very low through secondary purification processes, resulting in incomplete removal. Therefore, selecting the optimal method to remove these color compounds is essential. In this study, we studied the removal of an organic dye contaminant (Reactive Blue dye 19 [RB19]) using advanced oxidation processes (AOPs). For this purpose, ultraviolet (UV) mercury lamps with a wavelength of 254 nm and a voltage of W16 inside a reactor were used as an energy source. The experiments were performed in a collimated beam reactor inside a dark chamber. Two oxidizers, sodium hypochlorite (NaOCl) and hydrogen peroxide (H₂O₂), were used to remove RB19 from the artificial sewage stream. Removal of RB19 with a concentration of 20 mg/L with variable pH (5, 7, and 9), oxidant concentrations (5, 10, and 20 mg/L), and time (5, 10, 15, and 30 min) were investigated during the processes of photolysis, chemical oxidation (by H₂O₂ and NaOCl), and UV/NaOCl and UV/H₂O₂ AOPs. The photolysis process did not remove the RB19. The highest removal efficiencies of RB19 by chemical oxidation processes with NaOCl and H₂O₂, UV/NaOCl, and UV/H₂O₂ at optimal conditions (pH = 5, [oxidant] = 20 mg/L, RB19 = 20 mg/L, and radiation intensity of 1005 mJ/cm²) were 64.49%, 0.88%, 99.7%, and 13.31%, respectively. These results indicate that the hydroxyl radical was produced, under optimum conditions, more in the acidic medium; thus, the RB19 removal efficiency was higher in the acidic medium. The combination of UV rays with oxidants resulted in the production of more hydroxyl radicals and increased removal efficiency.     

A review of dark fermentative hydrogen production from biodegradable municipal waste fractions

Hydrogen is believed to play a potentially key role in the implementation of sustainable energy production, particularly when it is produced from renewable sources and low energy-demanding processes. In the present paper an attempt was made at critically reviewing more than 80 recent publications, in order to harmonize and compare the available results from different studies on hydrogen production from FW and OFMSW through dark fermentation, and derive reliable information about process yield and stability in view of building related predictive models. The review was focused on the effect of factors, recognized as potentially affecting process evolution (including type of substrate and co-substrate and relative ratio, type of inoculum, food/microorganisms [F/M] ratio, applied pre-treatment, reactor configuration, temperature and pH), on the fermentation yield and kinetics. Statistical analysis of literature data from batch experiments was also conducted, showing that the variables affecting the H₂ production yield were ranked in the order: type of co-substrate, type of pre-treatment, operating pH, control of initial pH and fermentation temperature. However, due to the dispersion of data observed in some instances, the ambiguity about the presence of additional hidden variables cannot be resolved. The results from the analysis thus suggest that, for reliable predictive models of fermentative hydrogen production to be derived, a high level of consistency between data is strictly required, claiming for more systematic and comprehensive studies on the subject.     

Investigation of the effect of culture type on biological hydrogen production from sugar industry wastes

The bio-hydrogen generation potential of sugar industry wastes was investigated. In the first part of the study, acidogenic anaerobic culture was enriched from the mixed anaerobic culture (MAC) through acidification of glucose. In the second part of the study, glucose acclimated acidogenic seed was used, along with the indigenous microorganisms, MAC, 2-bromoethanesulfonate treated MAC and heat treated MAC. Two different COD levels (4.5 and 30 g/L COD) were investigated for each culture type. Reactors with initial COD concentration of 4.5 g/L had higher H₂ yields (20.3–87.7 mL H₂/g COD) than the reactors with initial COD concentration of 30 g/L (0.9–16.6 mL H₂/g COD). The 2-bromoethanesulfonate and heat treatment of MAC inhibited the methanogenic activity, but did not increase the H₂ production yield. The maximum H₂ production (87.7 mL H₂/g COD) and minimum methanogenic activity were observed in the unseeded reactor with 4.5 g/L of initial COD.