Analysis of Products Generated from the Thermal and Catalytic Degradation of Pure and Waste Polyolefins using Py-GC/MS

The possibility of transforming waste plastics into valuable hydrocarbons via catalytic cracking and reforming is attracting increasing interest. Pyrolysis coupled with Gas Chromatographic separation and Mass Spectrometry detection (Py-GC/MS) has been used in this work to study the product selectivity of various catalysts in the conversion of pure and residual polyethylene samples into hydrocarbon products. Five acid solids of comparable aluminium contents but different textural and acid properties were tested as catalysts, including three zeolites (standard ZSM-5, nanocrystalline n-ZSM-5 and Beta) and two mesostructured solids (Al-MCM-41 and Al-SBA-15). Thermal cracking of the pure and residual polymers generated a similar range of products to each other, with a high proportion of linear paraffins and olefins of varying lengths. The presence of zeolitic materials resulted in complete elimination of heavy linear products, an increase in the light hydrocarbon fraction and a marked selectivity towards the formation of single-ring aromatic species, particularly benzene, toluene and xylene. Aromatic formation was particularly notable with the small crystal size n-ZSM-5 (aromatic selectivity up to 53.9%) and less marked in the case of standard ZSM-5 (up to 36.4%) and Beta zeolite (up to 35.0%). Mesostructured catalysts like Al-MCM-41 and Al-SBA-15 favoured the production of light C₂–C₅ hydrocarbons (up to 57.9%) while the formation of aromatic products was significantly lower than with zeolitic materials. The paper examines the extent and the causes for this product selectivity and discusses its connection with the acid and textural properties of each catalyst. It was also observed that, under the experimental conditions employed, the products generated were not significantly affected by the nature and origin of the polymers employed.     

Effect of Decalin Solvent on the Thermal Degradation of HDPE

The thermal cracking of HDPE in presence of different amounts of decalin was studied and compared with the reaction carried out in the absence of solvent. The decalin favours the mass and heat transfer during the reaction. In addition, it modifies the thermal degradation mechanism, which facilitates the formation of specific products. The use of decalin substantially increases the C₅–C₃₂ yield in comparison with the solventless reaction. In all cases, linear hydrocarbons such as n-paraffins, α-olefins and α,ω-dienes were detected. Increasing the decalin/plastic ratio led to enhanced α-olefin and n-paraffins yields, but the increase was more significant in the case of α-olefins, which are valuable compounds useful as raw chemicals. A reaction mechanism was proposed to explain the results obtained in presence of decalin. In these reactions, intramolecular radical transfer, secondary radical β-scission and hydrogen transfer from both decalin to intermediate radicals and from the polymer chain to regenerate the decalin play a significant role in determining the plastic conversion and the relative amounts of each product.     

Sequential extraction of 226Ra in sediments from an estuary affected historically by anthropogenic inputs of natural radionuclides

Riverbed sediments from an estuary historically affected by wastes discharged by several phosphate fertiliser plants and enriched in uranium-series radionuclides were operationally speciated using a Tessier-based method. In each selective fraction the (226)Ra content was determined by alpha-particle spectrometry after radiochemical isolation and electrodeposition onto stainless steel planchets. These studies were performed in (226)Ra-polluted estuarine sediments collected one year after anthropogenic discharges had ceased in order to obtain useful information about the operational forms in which this radionuclide remains associated with the sediments at this time. The results obtained revealed that one year after (226)Ra inputs had stopped, the radionuclide was associated mostly with the more refractory forms. Consequently, it is possible to foresee little potential remobilisation of (226)Ra contamination from sediments to the aqueous phase in the future under normal environmental conditions.     

Development of a framework for fire risk assessment using remote sensing and geographic information system technologies

Forest fires play a critical role in landscape transformation, vegetation succession, soil degradation and air quality. Improvements in fire risk estimation are vital to reduce the negative impacts of fire, either by lessen burn severity or intensity through fuel management, or by aiding the natural vegetation recovery using post-fire treatments. This paper presents the methods to generate the input variables and the risk integration developed within the Firemap project (funded under the Spanish Ministry of Science and Technology) to map wildland fire risk for several regions of Spain. After defining the conceptual scheme for fire risk assessment, the paper describes the methods used to generate the risk parameters, and presents proposals for their integration into synthetic risk indices. The generation of the input variables was based on an extensive use of geographic information system and remote sensing technologies, since the project was intended to provide a spatial and temporal assessment of risk conditions. All variables were mapped at 1 km² spatial resolution, and were integrated into a web-mapping service system. This service was active in the summer of 2007 for semi-operational testing of end-users. The paper also presents the first validation results of the danger index, by comparing temporal trends of different danger components and fire occurrence in the different study regions.     

Kinetics of scrap tyre pyrolysis under vacuum conditions

Scrap tyre pyrolysis under vacuum is attractive because it allows easier product condensation and control of composition (gas, liquid and solid). With the aim of determining the effect of vacuum on the pyrolysis kinetics, a study has been carried out in thermobalance. Two data analysis methods have been used in the kinetic study: (i) the treatment of experimental data of weight loss and (ii) the deconvolution of DTG (differential thermogravimetry) curve. The former allows for distinguishing the pyrolysis of the three main components (volatile components, natural rubber and styrene–butadiene rubber) according to three successive steps. The latter method identifies the kinetics for the pyrolysis of individual components by means of DTG curve deconvolution. The effect of vacuum in the process is significant. The values of activation energy for the pyrolysis of individual components of easier devolatilization (volatiles and NR) are lower for pyrolysis under vacuum with a reduction of 12 K in the reaction starting temperature. The kinetic constant at 503 K for devolatilization of volatile additives at 0.25 atm is 1.7 times higher than that at 1 atm, and that corresponding to styrene–butadiene rubber at 723 K is 2.8 times higher. Vacuum enhances the volatilization and internal diffusion of products in the pyrolysis process, which contributes to attenuating the secondary reactions of the repolymerization and carbonization of these products on the surface of the char (carbon black). The higher quality of carbon black is interesting for process viability.The large-scale implementation of this process in continuous mode requires a comparison to be made between the economic advantages of using a vacuum and the energy costs, which will be lower when the technologies used for pyrolysis require a lower ratio between reactor volume and scrap tyre flow rate.     

Alkylphenols and polycyclic aromatic hydrocarbons in eastern Mediterranean Spanish coastal marine bivalves

This paper reports the first results on alkylphenol pollution in edible bivalves from the Spanish coast. Two sampling campaigns (July 2006 and July 2007) were carried out to determine the concentration of nonylphenol (NP), octylphenol (OP), and eight polycyclic aromatic hydrocarbons (PAHs) in wild mussels (Mytilus galloprovincialys) and clams (Donax trunculus) at 14 sampling sites along the eastern Mediterranean Spanish coast. The results show that NP is the predominant alkylphenol, being the port of Valencia the most polluted area (up to 147 ??g/kg wet weight in clams). Moving away from the ports the concentration of NP in bivalves decreased. OP concentration was below its detection limit in most of the studied areas and its maximum concentration (6 ??g/kg w/w) was measured in clams from the port of Sagunto. The presence of low levels of PAHs was observed in most of the studied areas. The total PAHs concentration (i.e., sum of the eight measured PAHs) achieved a maximum value of 10.09 ??g/kg w/w in the north coast of Valencia city. The distribution pattern of the individual PAHs showed that both pollution sources petrogenic and pyrolytic were present in the sampled areas. Fluoranthene was the most abundant PAH in mussels while benzo(b)fluoranthene in clams. The maximum concentration of 10 ??g/kg w/w for benzo(a)pyrene established by the European Commission was never reached, indeed sampled bivalves showed concentrations 10 times lower than this reference value. Thus, they can be considered safe for human consumption. Despite the low contamination levels, the results show an overall pollution of bivalves by alkylphenol and PAHs as well as an increment in the number of polluted areas from 2006 to 2007. Thus, periodical sampling campaigns should be carried out to monitor the long-term tendency of these toxic and persistent pollutants.     

Chemical depolymerisation of PET complex waste: hydrolysis vs. glycolysis

The huge increase in the generation of post-consumer plastic waste has produced a growing interest in eco-efficient strategies and technologies for their appropriate management and recycling. In response to this, PROQUIPOL Project is focused on developing, optimizing and adapting feedstock recycling technologies as an alternative for management for the treatment of complex plastic waste. Among the different plastic wastes studied, PROQUIPOL Project is working on providing a suitable treatment to the highly colored and complex multilayered post-consumer waste fractions of polyethylene terephthalate (PET) by chemical depolymerisation methods. Glycolysis and alkali hydrolysis processes have been studied with the aim of promoting the transformation of PET into the bis(2-hydroxyethyl) terephthalate monomer and terephthalic acid, respectively. In both cases operational conditions such as temperature, reaction time, catalyst to PET rate and solvent to PET rate have been considered to optimize product yield, achieving values near to 90 % and monomer purities over 95 % in both processes. This paper presents results obtained for each treatment as well as a simplified comparison of technical, economic and environmental issues.     

Transportation fuel production by combination of LDPE thermal cracking and catalytic hydroreforming

Fuel production from plastics is a promising way to reduce landfilling rates while obtaining valuable products. The usage of Ni-supported hierarchical Beta zeolite (h-Beta) for the hydroreforming of the oils coming from LDPE thermal cracking has proved to produce high selectivities to gasoline and diesel fuels (>80%). In the present work, the effect of the Ni loading on Ni/h-Beta is investigated in the hydroreforming of the oils form LDPE thermal cracking. h-Beta samples were impregnated with Ni nitrate, calcined and reduced in H₂ up to 550 °C to achieve different Ni contents: 1.5%, 4%, 7% and 10%. Larger and more easily reducible metal particles were obtained on Ni 7%/h-Beta and Ni 10%/h-Beta. Hydroreforming tests were carried out in autoclave reactor at 310 °C, under 20 bar H₂, for 45 min. Ni content progressively increased the amount of gases at the expenses of diesel fractions, while gasoline remained approximately constant about 52–54%. Maximum selectivity to automotive fuels (～81%) was obtained with Ni 7%/h-Beta. Ni loading also enhanced olefins saturation up to Ni 7%/h-Beta. High cetane indices (71–86) and octane numbers (89–91) were obtained over all the catalysts. Regarding the different studied Ni contents, Ni 7%/h-Beta constitutes a rather promising catalyst for obtaining high quality fuels from LDPE thermal cracking oils.     

Hydroreforming over Ni/H-beta of the thermal cracking products of LDPE, HDPE and PP for fuel production

The thermal cracking at 400?°C of pure polyolefins—low density polyethylene (LDPE), high density polyethylene (HDPE) and polypropylene (PP) and a standard polyolefin mixture (46?% LDPE?+?27?% HDPE?+?28?% PP)—was studied together with the catalytic hydroreforming of the obtained oils over Ni/h-beta at 310?°C under 20?bar of hydrogen. The oils obtained after the thermal cracking of PP contain the highest amount of gasoline (58?%), while those coming from HDPE the lowest (39?%). The bromine index of the oils was very high, ranging from 54.1 (LDPE) to 83.8 (PP), indicating a high olefinic content of the oils. Additionally, the thermal cracking of the mixture indicates the occurrence of a synergestic effect among plastics, with transfer of methyl groups from PP to polyethylenes. Ni/h-beta (Si/Al?=?25; Ni content?=?6.2?wt%) catalyst was used in the hydroreforming since it contains a bimodal pore size distribution (0.6/3.1?nm), which improves accessibility of the oil molecules to the catalytic sites. After the hydroreforming and regardless of the plastics used, the share of lighter products (gasoline and gases) increases, reaching a remarkable 68?% of gasolines with the oils coming from PP. Regardless of the starting feed, the amount of useful fuels (gasoline?+?light diesel) was within 80–85?%. Additionally, the oils were successfully hydrogenated since the bromine indexes dropped below 7, indicating that more than 90?% of the starting olefins were saturated. The usage of catalysts increased the amount of aromatics in the obtained oils within 13–20?%, depending on the starting plastic. Likewise, the isoparaffin content of the gasolines was within 35–40?%, except for PP, where it was enhanced to 62?%. However, the research octane number (RON) of the gasolines from LDPE and PP and the cetane indexes of the diesel from all the plastics were promising for their application as fuels.     

AQUIFER MANAGEMENT UNDER TRANSIENT AND STEADY-STATE CONDITIONS1

ABSTRACT: The equations of transient and steady-state flow in two-dimensional artesian aquifers are approximated using finite differences. The resulting linear difference equations, combined with other linear physical and management constraints and a linear objective function, comprise a linear programming (LP) formulation. Solutions of such LP models are used to determine optimal well distributions and pumping rates to meet given management objectives for a hypothetical transient problem and for a steady-state field problem.