Sustainable processes using heterogeneous acid catalysts. Some examples of industrial interest.

In recent years the need for the design of more sustainable processes and the development of alternative reaction routes to reduce the environmental impact of the chemical industry has gained vital importance. Main objectives especially regard the use of renewable raw materials, the exploitation of alternative energy sources, the design of inherently safe processes and of integrated reaction/separation technologies (e.g. microreactors and membranes), the process intensification, the reduction of waste and the development of new catalytic pathways. The present PhD thesis reports results derived during a three years research period at the School of Chemical Sciences of Alma Mater Studiorum-University of Bologna, Dept. of Industrial Chemistry and Materials (now Dept. of Industrial Chemistry “Toso Montanari”), under the supervision of Prof. Fabrizio Cavani (Catalytic Processes Development Group). Three research projects in the field of heterogeneous acid catalysis focused on potential industrial applications were carried out. The main project, regarding the conversion of lignocellulosic materials to produce monosaccharides (important intermediates for production of biofuels and bioplatform molecules) was financed and carried out in collaboration with the Italian oil company eni S.p.A. (Istituto eni Donegani-Research Center for non-Conventional Energies, Novara, Italy) The second and third academic projects dealt with the development of green chemical processes for fine chemicals manufacturing. In particular, (a) the condensation reaction between acetone and ammonia to give triacetoneamine (TAA), and (b) the Friedel-Crafts acylation of phenol with benzoic acid were investigated.

Waste management in Forlì-Cesena province: Life Cycle Assessment (LCA) of Forlì incinerator

This work assesses the environmental impact of a municipal solid waste incinerator with energy recovery in Forlì-Cesena province (Emilia-Romagna region, Italy). The methodology used is Life Cycle Assessment (LCA). As the plant already applies the best technologies available in waste treatment, this study focuses on the fate of the residues (bottom and fly ash) produced during combustion. Nine scenarios are made, based on different ash treatment disposing/recycling techniques. The functional unit is the amount of waste incinerated in 2011. Boundaries are set from waste arrival in the plant to the disposal/recovery of the residues produced, with energy recovery. Only the operative period is considered. Software used is GaBi 4 and the LCIA method used is CML2001. The impact categories analyzed are: abiotic depletion, acidification, eutrophication, freshwater aquatic ecotoxicity, global warming, human toxicity, ozone layer depletion, photochemical oxidant formation, terrestrial ecotoxicity and primary energy demand. Most of the data are taken from Herambiente. When primary data are not available, data from Ecoinvent and GaBi databases or literature data are used. The whole incineration process is sustainable, due to the relevant avoided impact given by co-generator. As far as regards bottom ash treatment, the most influential process is the impact savings from iron recovery. Bottom ash recycling in road construction or as building material are both valid alternatives, even if the first option faces legislative limits in Italy. Regarding fly ash inertization, the adding of cement and Ferrox treatment results the most feasible alternatives. However, this inertized fly ash can maintain its hazardous nature. The only method to ensure the stability of an inertized fly ash is to couple two different stabilization treatments. Ash stabilization technologies shall improve with the same rate of the flexibility of the national legislation about incineration residues recycling.

Valorisation of organic waste: new developments from proton nuclear magnetic resonance characterization

The last half-century has seen a continuing population and consumption growth, increasing the competition for land, water and energy. The solution can be found in the new sustainability theories, such as the industrial symbiosis and the zero waste objective. Reducing, reusing and recycling are challenges that the whole world have to consider. This is especially important for organic waste, whose reusing gives interesting results in terms of energy release. Before reusing, organic waste needs a deeper characterization. The non-destructive and non-invasive features of both Nuclear Magnetic Resonance (NMR) relaxometry and imaging (MRI) make them optimal candidates to reach such characterization. In this research, NMR techniques demonstrated to be innovative technologies, but an important work on the hardware and software of the NMR LAGIRN laboratory was initially done, creating new experimental procedures to analyse organic waste samples. The first results came from soil-organic matter interactions. Remediated soils properties were described in function of the organic carbon content, proving the importance of limiting the addition of further organic matter to not inhibit soil processes as nutrients transport. Moreover NMR relaxation times and the signal amplitude of a compost sample, over time, showed that the organic matter degradation of compost is a complex process that involves a number of degradation kinetics, as a function of the mix of waste. Local degradation processes were studied with enhanced quantitative relaxation technique that combines NMR and MRI. The development of this research has finally led to the study of waste before it becomes waste. Since a lot of food is lost when it is still edible, new NMR experiments studied the efficiency of conservation and valorisation processes: apple dehydration, meat preservation and bio-oils production. All these results proved the readiness of NMR for quality controls on a huge kind of organic residues and waste.

Cascading events triggering industrial accidents: quantitative assessment of NaTech and domino scenarios

The so called cascading events, which lead to high-impact low-frequency scenarios are rising concern worldwide. A chain of events result in a major industrial accident with dreadful (and often unpredicted) consequences. Cascading events can be the result of the realization of an external threat, like a terrorist attack a natural disaster or of “domino effect”. During domino events the escalation of a primary accident is driven by the propagation of the primary event to nearby units, causing an overall increment of the accident severity and an increment of the risk associated to an industrial installation. Also natural disasters, like intense flooding, hurricanes, earthquake and lightning are found capable to enhance the risk of an industrial area, triggering loss of containment of hazardous materials and in major accidents. The scientific community usually refers to those accidents as “NaTechs”: natural events triggering industrial accidents. In this document, a state of the art of available approaches to the modelling, assessment, prevention and management of domino and NaTech events is described. On the other hand, the relevant work carried out during past studies still needs to be consolidated and completed, in order to be applicable in a real industrial framework. New methodologies, developed during my research activity, aimed at the quantitative assessment of domino and NaTech accidents are presented. The tools and methods provided within this very study had the aim to assist the progress toward a consolidated and universal methodology for the assessment and prevention of cascading events, contributing to enhance safety and sustainability of the chemical and process industry.

Hazardous air pollutants and childhood lymphohematopoietic cancer in Southeast Texas, 1995--2004

Southeast Texas, including Houston, has a large presence of industrial facilities and has been documented to have poorer air quality and significantly higher cancer rates than the remainder of Texas. Given citizens’ concerns in this 4th largest city in the U.S., Mayor Bill White recently partnered with the UT School of Public Health to determine methods to evaluate the health risks of hazardous air pollutants (HAPs). Sexton et al. (2007) published a report that strongly encouraged analytic studies linking these pollutants with health outcomes. In response, we set out to complete the following aims: 1. determine the optimal exposure assessment strategy to assess the association between childhood cancer rates and increased ambient levels of benzene and 1,3-butadiene (in an ecologic setting) and 2. evaluate whether census tracts with the highest levels of benzene or 1,3-butadiene have higher incidence of childhood lymphohematopoietic cancer compared with census tracts with the lowest levels of benzene or 1,3-butadiene, using Poisson regression. The first aim was achieved by evaluating the usefulness of four data sources: geographic information systems (GIS) to identify proximity to point sources of industrial air pollution, industrial emission data from the U.S. EPA’s Toxic Release Inventory (TRI), routine monitoring data from the U.S. EPA Air Quality System (AQS) from 1999-2000 and modeled ambient air levels from the U.S. EPA’s 1999 National Air Toxic Assessment Project (NATA) ASPEN model. Further, once these four data sources were evaluated, we narrowed them down to two: the routine monitoring data from the AQS for the years 1998-2000 and the 1999 U.S. EPA NATA ASPEN modeled data. We applied kriging (spatial interpolation) methodology to the monitoring data and compared the kriged values to the ASPEN modeled data. Our results indicated poor agreement between the two methods. Relative to the U.S. EPA ASPEN modeled estimates, relying on kriging to classify census tracts into exposure groups would have caused a great deal of misclassification. To address the second aim, we additionally obtained childhood lymphohematopoietic cancer data for 1995-2004 from the Texas Cancer Registry. The U.S. EPA ASPEN modeled data were used to estimate ambient levels of benzene and 1,3-butadiene in separate Poisson regression analyses. All data were analyzed at the census tract level. We found that census tracts with the highest benzene levels had elevated rates of all leukemia (rate ratio (RR) = 1.37; 95% confidence interval (CI), 1.05-1.78). Among census tracts with the highest 1,3-butadiene levels, we observed RRs of 1.40 (95% CI, 1.07-1.81) for all leukemia. We detected no associations between benzene or 1,3-butadiene levels and childhood lymphoma incidence. This study is the first to examine this association in Harris and surrounding counties in Texas and is among the first to correlate monitored levels of HAPs with childhood lymphohematopoietic cancer incidence, evaluating several analytic methods in an effort to determine the most appropriate approach to test this association. Despite recognized weakness of ecologic analyses, our analysis suggests an association between childhood leukemia and hazardous air pollution.^

Industrial benzene emissions in Houston: Legal barriers to reducing a public health threat

Decades of research show that environmental exposure to the chemical benzene is associated with severe carcinogenic, hematoxic and genotoxic effects on the human body. As such, the Environmental Protection Agency (EPA) has designated the chemical as a Hazardous Air Pollutant and prescribed benzene air concentration guidelines that provide cities with an ideal ambient level to protect human health. However, in Houston, Texas, a city home to the top industrial benzene emitters in the US who undoubtedly contribute greatly to the potentially unsafe levels of ambient benzene, regulations beyond the EPA’s unenforceable guidelines are critical to protecting public health. Despite this, the EPA has failed to establish National Ambient Air Quality Standards (NAAQS) for benzene. States are thus left to regulate air benzene levels on their own; in the case of Texas, the Texas Commission on Environmental Quality (TCEQ) and state legislature have failed to proactively develop legally enforceable policies to reduce major source benzene emissions. This inaction continues to exacerbate a public health problem, which may only be solved through a legal framework that restricts preventable benzene emissions to protect human health and holds industrial companies accountable for violations of such regulations and standards. This analysis explores legal barriers that the City of Houston and other relevant agencies currently face in their attempt to demand and bring about such change. ^

Reverse logistics systems for waste generated throughout vehicles life-cycle

Waste produced during the service life of automobiles has received much less attention than end-of-life vehicles themselves. In this paper, we deal with the set up of a reverse logistics system for the collection and treatment of use-phase residues. First, the type of waste arising during vehicles? service life is characterized. Data were collected in collaboration with SIGRAUTO, the product stewardship organization in charge of vehicles? recovery in Spain. Next, three organizational models are proposed. The three alternatives are benchmarked and assessed from a double organizational and operational perspective for the particular case of the Madrid region in Spain

Effects of biochar prepared from organic waste on soil properties

Biochar is a carbon-rich solid obtained by the thermal decomposition of organic matter under a limited supply of oxygen and at relatively low temperatures. Biochar can be prepared from the pyrolysis of different organic feed- stocks, such as wood and biomass crops, agricultural by-products, different types of waste or paper industry waste materials . The pyrolysis procedure of waste, i.e. sewage sludge, has mainly two advantages, firstly, it removes pathogens from waste and, secondly, biochar can reduce the leaching of heavy metals present in raw sewage sludge. This trend of the use of waste material as feedstocks to the preparation of biochar is increasing in the last years due to industrial development and economic growth imply an increase in waste generation. The application of biochar may have positive effects on soil physical properties as water holding capacity and structure or on soil biological activity and soil quality. Also, biochar can be used to remove water pollutants and can be used in multiple ways in soil remediation due to its adsorption of pesticides or metals. Also, biochar contribute to carbon sequestration due to carbon stability of biochar materials. The objective of this presentation is to review the positive effects of the biochar prepared from organic waste on soil properties.

Análisis de la degradación, desintegración y biodegradabilidad de bolsas de poliéster y almidón en compostaje de residuos urbanos: escalas de laboratorio e industrial

El principal objetivo de esta tesis es verificar que las bolsas biodegradables de copoliéster (PBAT) con base de almidón (UNE 13432: 2001) alcanzan los niveles de degradación y desintegración requeridos para su certificación (%D= ≥ 90%), medido en condiciones reales de compostaje industrial. Para lograr mayor representatividad, los ensayos se han realizado en dos plantas de tratamiento de residuos urbanos en las que se aplican las técnicas de compostaje más comunes en el ámbito europeo y nacional, pila y túnel, mediante el compostaje de la FORSU. Se llevaron a cabo dos tipos de ensayos. Por un lado se realizó un ensayo escala de laboratorio (ISO 14855), orientado como indicador de la biodegradabilidad del polímero en el formato bolsa comercializado. Por otro lado, se desarrollaron una batería de ensayos realizados en dos plantas de compostaje de residuos urbanos: el Centro de Tratamiento de Residuos de Torija (Ávila), que realiza el compostaje mediante pila volteada, y el Centro de Tratamiento de Residuos de Arenas de San Pedro (Ávila), que realiza el compostaje en túnel. Para la obtención de resultados se han contrastado parámetros como el porcentaje de biodegradación (%B), el porcentaje de desintegración (%D), degradación superficial de las muestras, calidad de la FORSU inicial (caracterizaciones y análisis físico-químico) y calidad del MB final (análisis físico-químico e IG). Atendiendo al objetivo general se demuestra que las bolsas de copoliéster con base de almidón certificadas (UNE EN 13432:2001) han alcanzado el 94,37% ± 0,007% de desintegración en la planta de compostaje de FORSU con pila volteada; y el 86,36% ± 0,151% en la planta de compostaje de FORSU con túnel estático. A pesar de la aparente diferencia, el resultado del análisis concluye que no existen diferencias estadísticamente significativas entre técnicas de compostaje. La presencia de impropios y el contendido de metales pesados en la FORSU no han influido en la desintegración de las bolsas de estudio. En cambio, se ha detectado una influencia estadísticamente significativa entre el contenido de materia orgánica total y de nutrientes de la FORSU y el porcentaje de desintegración de las muestras. No se detectado una relación estadísticamente significativa entre la presencia de bolsas de estudio en las concentraciones definidas, y la calidad del MB, medido mediante el análisis físico-químico, microbiológico y el IG del MB. La concentración de los metales pesados en la mayoría de las muestras de material bioestabilizado cumplió con los límites establecidos para la categoría A, aplicable al “compost” procedente de la fracción orgánica recogida de forma separada según el RD 506/2013 de productos fertilizantes. También se detectó fitotoxicidad alta (FA) según la metodología y criterios de valoración definidos. Esta fitotoxicidad no está relacionada con la presencia de las bolsas de estudio sino con la calidad de la FORSU de partida y/o con los productos liberados durante el proceso de compostaje. ABSTRACT The main objective of this thesis is to verify that the copolyester (PBAT) starch based (UNE 13432: 2001) biodegradable bags reach levels of degradation and disintegration required for it´s certification (% D = ≥ 90%), measured in terms of real industrial composting. The tests were performed at two municipal solid waste (MSW) treatment plants, where the most common composting techniques applied at European and national level were represented, windrow and tunnel. Two types of tests were carried out: First, a laboratory scale test (ISO 14855), as an indicator of the polymer biodegradation of the commercialized bag format. Second, a battery of tests was conducted at two MSW composting plants, Waste Treatment Center of Torija (Guadalajara), that makes compost by turned pile, and the Waste Treatment Center of Arenas de San Pedro (Ávila), where makes compost by static tunnel. To obtain the results, the parameters such as the biodegradation percentage (% B), the disintegration percentage (% D), surface degradation of the samples, the initial quality of FORSU (characterizations and physico-chemical analysis) and bioestabilithated material (MB) quality (physico-chemical analysis and IG) have been compared. In reference to the general aim It shows that the copolyester starch based certified (UNE-EN 13432) bags have reached 94.37% ± 0.007% of disintegration in the composting turned pile; and 86.36% ± 0.151% in the static tunnel. Despite the apparent difference, the result of the analysis concludes that there are no statistically significant differences between composting techniques. The presence of non-compostable materials and the heavy metals content in the FORSU has not affected in the disintegration of the bags. Instead, It has been detected a statistically significant influence over the total organic matter content and nutrient content in the FORSU and the samples disintegration percentage. A statistically significant relationship between the bag presence in the defined concentrations and the quality of MB measured by physical-chemical analysis, microbiological analysis and IG of the MB is not detected. The concentration of heavy metals in most MB samples was within the limits of A-Class, applicable to "compost" from organic waste collected separately according to RD 506/2013 of fertilizers. High phytotoxicity (FA) was also detected according to the methodology and evaluation defined. The phytotoxicity is not related to the presence of bags but it is with the FORSU initial quality and/or with the products released during the composting process.

Development of a Household Pharmaceutical Waste Collection Program for Atlanta, Georgia: An Analysis of Risk Factors and Public Awareness with a Comprehensive Collection Plan

Decades of mixed messages from three federal agencies left many Americans unaware of the hazards associated with the indiscriminate disposal of unwanted or expired medicines. For this Capstone project, a systematic review of state and federal regulations was undertaken to determine how these laws obstruct household pharmaceutical waste collection. In addition, a survey of 654 Atlanta residents was conducted to evaluate unwanted medicine disposal habits, awareness of pharmaceutical compounds being detected in drinking water, surface, and ground waters, and willingness to participate in a household pharmaceutical waste collection program. Survey responses were tabulated to provide overall results and by age group, gender, and race. A household pharmaceutical waste collection plan was developed for the city and included as an appendix.

Emissions of Gases, Polycyclic Aromatic Hydrocarbons and Brominated Pollutants during Thermal Degradation of Waste Printed Circuit Boards

Resumen del póster presentado en Symposium on Renewable Energy and Products from Biomass and Waste, CIUDEN (Cubillos de Sil, León, Spain), 12-13 May 2015

Forecasts of the quantity and composition of solid waste /

"Contract no. 68-03-2649."

Selected methods for detecting and tracing hazardous materials spills /

Mode of access: Internet.

Laboratory investigation of residual liquid organics from spills, leaks, and the disposal of hazardous wastes in groundwater /

Mode of access: Internet.