The role of temperature profile during the pyrolysis of end-of-life-tyres in an industrially relevant conditions auger plant.

Pyrolysis is a chemical recycling process of interest as a means to achieve a sustainable circular economy for end-of-life tyres (ELTs). In the pyrolysis process, ELTs are converted into tyre pyrolysis gas (TPG), tyre pyrolysis oil (TPO) and raw recovered carbon black (RRCB). This work investigates for the first time the effect of different temperature profiles by using a single-auger pyrolysis reactor in an industrially relevant scale (TRL-5). Since the development of this process at this representative scale is quite limited and the temperature profile has not been previously studied, the results achieved in this work can provide a useful database for the development of this process at industrial scale. For this purpose, two different sources of ELTs, commercial truck tyres (CTTs) and passenger car tyres (PCTs), were used. Accordingly, the experimental campaign was conducted using two different incremental temperature profiles (425-550-775 °C and 600-700-800 °C) based on those that can be replicated in an industrial-scale auger pyrolysis plant. For the sake of comparison, two isothermal heating conditions (500-500-500 °C and 600-600-600 °C) were also tested. The results confirmed the remarkable influence of temperature profile on both the distribution and properties of products. The 425-550-775 °C temperature profile was found to enhance limonene production, which is associated with the minimisation of secondary reactions in the first heating zone of the reactor. Additionally, there were very low carbonaceous deposits found in the RRCB because of the high severity of devolatilisation conditions in the third heating zone of the reactor. On the other hand, when the temperature profile was raised, the production of single-ring aromatics, particularly benzene, toluene, ethylbenzene and xylenes (BTEX) significantly increased in the TPO at the expense of limonene. Thus, from this strategy, it is possible to tune the properties of the products depending on the requirements of the application in a single step, getting closer for circular economy in the ELT recycling domain.

On Fractioning the Tire Pyrolysis Oil in a Pilot-Scale Distillation Plant under Industrially Relevant Conditions.

Tire pyrolysis oil (TPO) is one of the most interesting products derived from the pyrolysis of end-of-life tires. Among others, it contains valuable chemicals, such as benzene, toluene, ethylbenzene, and xylene (BTEX), as well as limonene. In order to recover these chemicals, a pilot-scale distillation plant has been designed, erected, and operated using TPO derived from an industrial-scale pyrolysis plant. The distillation facility consists of a packed column (20 kg/h) and is within the fifth technological readiness level. This work describes for the first time the fractioning of the TPO in a continuous operational mode under industrially relevant conditions. For this purpose, different reboiler temperatures (250-290 °C) and reflux ratios (up to 2.4) were preliminarily assessed on the yields and properties of the resulting products: light fraction (LF) and heavy fraction (HF). Thus, the distillation plant is capable of producing 27.0-36.7 and 63.3-73.0 wt % of LF and HF, respectively. The highest BTEX concentration in the LF (55.2 wt %) was found using a reboiler temperature of 250 °C and a reflux ratio of 2.4. Contrarily, the highest limonene concentration (4.9 wt %) in the LF was obtained at 290 °C in the reboiler without reflux. In this sense, the lower the reboiler temperature, the higher the BTEX, and the lower the limonene concentration in the LF. The main results herein obtained serve to gain key insights to operate packed distillation columns using complex and promising hydrocarbons as TPO in order to recover valuable products. In addition, this work provides significant information for optimizing the recovery efficiencies of both BTEX and limonene, as well as their potential applications including that for the resulting HF.

CO2 capture from cement plants using oxyfired precalcination and/or calcium looping.

This paper compares two alternatives to capture CO(2) from cement plants: the first is designed to exploit the material and energy synergies with calcium looping technologies, CaL, and the second implements an oxyfired circulating fluidized bed precalcination step. The necessary mass and heat integration balances for these two options are solved and compared with a common reference cement plant and a cost analysis exercise is carried out. The CaL process applied to the flue gases of a clinker kiln oven is substantially identical to those proposed for similar applications to power plants flue gases. It translates into avoided cost of of 23 $/tCO(2) capturing up to 99% of the total CO(2) emitted in the plant. The avoided cost of an equivalent system with an oxyfired CFBC precalcination only, goes down to 16 $/tCO(2) but only captures 89% of the CO(2) emitted in the plant. Both cases reveal that the application of CaL or oxyfired CFBC for precalcination of CaCO(3) in a cement plant, at scales in the order of 50 MWth (referred to the oxyfired CFB calciner) is an important early opportunity for the development of CaL processes in large scale industrial applications as well as for the development of zero emissions cement plants.

A pyrolysis process coupled to a catalytic cracking stage: A potential waste-to-energy solution for mattress foam waste.

Pyrolysis coupled to either thermal or catalytic cracking of mattress foam waste was performed in a laboratory-scale facility consisting of a fixed-bed reactor joined to a tubular cracking reactor. The results showed a great potential for the production of syngas specially at high cracking temperatures. Particularly, fixing 800 °C in the cracking reactor, a CO and CH4 rich gas with a remarkable amount of H2 was obtained. The addition of catalysts (dolomite, olivine or HiFUEL®) significantly decreased undesirable tar formation, (below 10 wt%), simultaneously increasing the gas yield and keeping CO and CH4 as the main components in the stream, becoming a preferable route that the non-catalytic process. Accordingly, this stream could be used preferably for further applications in energy generation because its heating value ranged between 15.7 MJ/Nm3 and 19.6 MJ/Nm3. In particular, the gas obtained by the use of dolomite could be advantageous for the production of organic compounds such as dimethyl ether (DME) as well as its use an engine or boiler to generate electricity in small facilities. In addition, the solid fraction obtained after de process could be used as a medium quality refused derived fuel (LHV ~ 12 MJ/kg) in order to support the internal energy requirements of the process.

A combined two-stage process of pyrolysis and catalytic cracking of municipal solid waste for the production of syngas and solid refuse-derived fuels.

Pyrolysis combined to either thermal cracking or catalytic cracking of municipal solid waste was performed in a laboratory-scale facility consisting of a fixed-bed reactor followed by a tubular cracking reactor. The results showed great potential for the production of syngas. The incorporation of inexpensive and widely available dolomite in the cracking reactor (with a constant feedstock to calcined dolomite ratio of 5:1) favoured the catalytic cracking of the primary pyrolysis products towards H2 and CO in a temperature range of 800-900 °C. More particularly, it was possible at 900 °C to achieve a syngas consisting of more than 80 vol% CO and H2 with a heating value of 16 MJ/Nm3. Additionally, a homogeneous solid fuel was obtained as a solid residue, which can be used to provide additional energy to support the process or as a refuse-derived fuel. Thus, the great potential of this process was demonstrated for turning municipal solid waste into a valuable gas fraction that can be used directly as a fuel or as a source of different value-added products.

Carbon black recovery from waste tire pyrolysis by demineralization: Production and application in rubber compounding.

Pyrolysis offers the possibility to convert waste tires into liquid and gaseous fractions as well as a carbon-rich solid (CBp), which contains the original carbon black (CB) and the inorganic compounds used in tire manufacture. Whilst both liquid and gaseous fractions can be valorized without further processing, there is a general consensus that CBp needs to be improved before it can be considered a commercial product, seriously penalizing the pyrolysis process profitability. In this work, the CBp produced in a continuous pyrolysis process was demineralized (chemical leaching) with the aim of recovering the CB trapped into the CBp and thus, producing a standardized CB product for commercial purposes. The demineralization process was conducted by using cheap and common reagents (HCl and NaOH). In this sense, the acid treatment removed most of the mineral matter contained in the CBp and concentration was the main parameter controlling the demineralization process. An ash content of 4.9 wt% was obtained by using 60 min of soaking time, 60 °C of temperature, 10 mL/g of reagent/CBp ratio and HCl 4 M. The demineralized CBp (dCBp) showed a carbon content of 92.9 wt%, while the FRX analysis indicated that SiO2 is the major component into the ash. The BET surface area was 76.3 m2/g, and textural characterizations (SEM/EDX and TEM) revealed that dCBp is composed by primary particles lower than 100 nm. Although dCBp showed a low structure, the surface chemistry was rich in surface acidic groups. Finally, dCBp was used in Styrene Butadiene Rubber (SBR) compounding, probing its technical feasibility as substitute of commercial CB N550.

Spatial and temporal PAH concentrations in Zaragoza, Spain.

The concentration of seven polycyclic aromatic hydrocarbons (PAH) associated with the atmospheric solid phase was measured in the Zaragoza (North-East of Spain) atmosphere using fluorescence spectroscopy in the synchronous mode (FS). The PAH results were reported for four different urban and suburban places, located within the city and during the period October 1999-September 2001. The PAH data obtained indicated the importance of local sources generated from urban/industrial areas. Although the PAH total concentration was quite similar in all the sampling sites, the main differences were due to Benzo[a]pyrene (BaP) and Coronene (Cor) concentrations, reaching the highest values in the sites associated with heavy traffic (trucks, lorries, etc.). The temporal evolution of atmospheric solid phase PAH concentrations indicated a seasonal trend. Higher PAH concentrations were found during colder seasons for the four sampling sites. The influence of environmental parameters such as temperature, rain, relative humidity, wind speed and direction on the PAH emissions was analyzed observing a positive correlation between the total PAH concentration and the relative humidity and a negative one with the temperature. With regard to the wind direction, higher PAH emissions were detected when wind was coming from an east and north-east direction. Wind from a north-westerly direction showed lower PAH emissions associated with the cierzo wind which provided cleaner air.

Demonstration of the waste tire pyrolysis process on pilot scale in a continuous auger reactor.

This work shows the technical feasibility for valorizing waste tires by pyrolysis using a pilot scale facility with a nominal capacity of 150 kWth. A continuous auger reactor was operated to perform thirteen independent experiments that conducted to the processing of more than 500 kg of shredded waste tires in 100 h of operation. The reaction temperature was 550°C and the pressure was 1 bar in all the runs. Under these conditions, yields to solid, liquid and gas were 40.5 ± 0.3, 42.6 ± 0.1 and 16.9 ± 0.3 wt.% respectively. Ultimate and proximate analyses as well as heating value analysis were conducted for both the solid and liquid fraction. pH, water content, total acid number (TAN), viscosity and density were also assessed for the liquid and compared to the specifications of marine fuels (standard ISO 8217). Gas chromatography was used to calculate the composition of the gaseous fraction. It was observed that all these properties remained practically invariable along the experiments without any significant technical problem. In addition, the reaction enthalpy necessary to perform the waste tire pyrolysis process (907.1 ± 40.0 kJ/kg) was determined from the combustion and formation enthalpies of waste tire and conversion products. Finally, a mass balance closure was performed showing an excellent reliability of the data obtained from the experimental campaign.

High activity mesoporous copper doped cerium oxide catalysts for the total oxidation of polyaromatic hydrocarbon pollutants.

The doping of mesoporous ceria with copper significantly enhances activity for naphthalene total oxidation, the enhanced performance is controlled by the increased concentration of surface oxygen defects.

Highly dispersed encapsulated AuPd nanoparticles on ordered mesoporous carbons for the direct synthesis of H2O2 from molecular oxygen and hydrogen.

AuPd nanoparticles (<3 nm) have been encapsulated on the pores of a nanostructured CMK-3 carbon prepared by a nanocasting procedure. This material has been shown to be an excellent catalyst for the direct synthesis of hydrogen peroxide from molecular hydrogen and oxygen.

Deep oxidation of pollutants using gold deposited on a high surface area cobalt oxide prepared by a nanocasting route.

Gold deposited on a cobalt oxide with high surface area (138 m(2)g(-1)), obtained through a nanocasting route using a siliceous KIT-6 mesoporous material as a hard template, has demonstrated high activity for the total oxidation of propane and toluene, and ambient temperature CO oxidation. The addition of gold promotes the activity when compared to a gold-free Co(3)O(4) catalyst prepared using the same nanocasting technique. The enhanced catalytic activity when gold is present has been explained for the deep oxidation of propane and toluene in terms of the improved reducibility of cobalt oxide when gold is added, rather than to the intrinsic activity of metallic gold particles. The improved behaviour for CO oxidation has been linked to the simultaneous presence of Au(δ+) and Au°.

Valorisation of forestry waste by pyrolysis in an auger reactor.

Pyrolysis of forestry waste has been carried out in an auger reactor to study the influence of operational variables on the reactor performance and the properties of the related products. Pine woodchips were used for the first time as raw material and fed continuously into the reactor. Ten experiments were carried out under inert atmosphere at: (i) different reaction temperature (1073, 973, 873, 823 and 773 K); (ii) different solid residence time (5, 3, 2 and 1.5 min); and (iii) different biomass flow rate (3.9, 4.8 and 6.9 kg/h). Results show that the greatest yields for liquid production (59%) and optimum product characterisation were obtained at the lowest temperature studied (773 K) and applying solid residence times longer than 2 min. Regarding bio-oil properties, GC/MS qualitative identification show that the most abundant compounds are volatile polar compounds, phenols and benzenediols; and very few differences can be observed among the samples regardless of the pyrolysis operating conditions. On the whole, experimental results demonstrate that complete reaction of forest woodchips can be achieved in an auger reactor in most of the experimental conditions tested. Moreover, this study presents the initial steps for the future scaling up of the auger reactor with the aim of converting it into a mobile plant which will be able to remotely process biomass such as energy crops, forestry and agricultural wastes to obtain bio-oil that, in turn, can be used as energy vector to avoid high transport costs.

Production of activated carbon by waste tire thermochemical degradation with CO2.

The thermochemical degradation of waste tires in a CO(2) atmosphere without previous treatment of devolatilization (pyrolysis) in order to obtain activated carbons with good textural properties such as surface area and porosity was studied. The operating variables studied were CO(2) flow rate (50 and 150 mL/min), temperature (800 and 900 degrees C) and reaction time (1, 1.5, 2, 2.5 and 3h). Results show a considerable effect of the temperature and the reaction time in the porosity development. Kinetic measurements showed that the reactions involved in the thermochemical degradation of waste tire with CO(2), are similar to those developed in the pyrolysis process carried out under N(2) atmosphere and temperatures below 760 degrees C, for particles sizes of 500 microm and heating rate of 5 degrees C/min. For temperatures higher than 760 degrees C the CO(2) starts to oxidize the remaining carbon black. Activated carbon with a 414-m(2)/g surface area at 900 degrees C of temperature, 150 mL/min of CO(2) volumetric flow and 180 min of reaction time was obtained. In this work it is considering the no reactivity of CO(2) for devolatilization of the tires (up to 760 degrees C), and also the partial oxidation of residual char at high temperature for activation (>760 degrees C). It is confirmed that there are two consecutive stages (devolatilization and activation) developed from the same process.

Total oxidation of naphthalene with high selectivity using a ceria catalyst prepared by a combustion method employing ethylene glycol.

During the catalytic combustion of naphthalene, compounds other than CO(2) are often obtained. These products, as polymerized polycyclic aromatic hydrocarbons, oxygenated aromatic compounds and benzene derivate compounds, are usually more toxic than naphthalene. At the present work it is shown a nanocrystalline cerium oxide prepared by a combustion method employing a proper ethylene glycol concentration that exhibits very high activity in the decomposition of naphthalene in the presence of air and, most importantly, a selectivity value towards CO(2) of 100% for any range of conversions and/or temperatures used. In addition, it has been demonstrated that the amount of ethylene glycol employed in the synthesis of the catalyst is determinant to achieve the optimal catalytic performance. The catalytic results have been explained in terms of the amount of cerium oxide defects.