Statistic data indicates that about 100,000 tones of waste tire were generated each year. Current recycling market of waste tire is very small. Therefore, many waste tires remain untreated and cause severe health and safety problems in storage. PP fiber cut end is the waste material after cutting off the fiber. Traditional reuse way was to be the toy¡¦s fillers. If we can reuse the materials properly to develop a market of additional value, it will be a big contribution to the society. In this research, recycled waste tire powder and PP fiber cut end are used as oil adsorbents for the purpose of oil recovery during the process of oil spill emergency response. PP fiber cut end and waste tire powder are capable of adsorbing oil due to their hydrophobic surface property and the capillary forces developed during the contact with oil, therefore, makes them a perfect material for oil recovery. The major advantage of recycled PP fiber cut end is its high oil adsorbing capacity (approximately 48.4g/g). But, after reuse, its oil adsorbing speed was slow down, so does the oil adsorbing capacity. On the other hand, with good elasticity, the waste tire powder can be reused for more than 100 times without loosing its capability. However, the oil adsorbing capacity of waste tire powder is far less than PP fiber (approximately 2.84g/g). Finally, we combine PP fiber cut end and waste tire powder, to see if we can take the advantage of each product and make the best utilization of the composite material. Results indicate the composite material can be reused for more than 100 times without loosing its capability, and its performance is even better than the combination of each individual product. In the other test, we can see the composite material can not only adsorb engine oil and crude oil, but also adsorb emulsified oil. In the test, the composite material can recover up to 28 times of its own weight of oil. With the invented set up, the oil recover work is much easier to operate, and moreover, the composite material is less expensive. Only a squeeze roller and a collection container are required to recover oil. So, the composite material is indeed having practicability and mobility. Finally, the composite material is an excellent adsorbent compares with other products available on the market.

This study investigated the production of powdered activated carbon derived from carbon black of pyrolyzed waste tires, and their adsorptive capacity on vapor-phase mercury chloride (HgCl2) using both adsorption column and thermogravimetric adsorption systems. The adsorption isotherms and kinetic models were further simulated in the study. In addition, an innovative compositive impregnation process was developed to increase the sulfur content of powdered activated carbon derived from waste tires. The activation of carbon black to form powdered activated carbon was performed in a tubular oven. The operating parameters including activation temperatures, activation time, and water feed rates were investigated in this study. Experimental results indicated that the yield of carbon-black derived powdered activated carbon (CBPAC) decreased with the increase of activation temperature, activation time, and water feed rate, while the BET surface area and pore volume decreased. In the comparison of activation time and water feed rate in the activation process, activation time had an important impact on the production of specific surface area than water feed rate. The optimal operating parameters included activation temperature of 900¢J, activation time of 180min, water feed rate of 0.5 mLH2O/gC-sec, and water injection behind activation process of 17.5 min. From the analysis of carbon surface, the carbon contents of powdered carbon black (PCB), CBPAC, commercial powdered activated carbon (CPAC) were 89.5%, 87.6%, and 88%, respectively. The C (1s) peak region of PCB consisted of 49.8% C-C, 38.9% C-O, 10.5% C=O or O-C-O. Similar analysis results showed that the total area of the C (1s) peak region of CBPAC consisted of 57.5% C-C, 26.8% C-O, 8.1% C=O or O-C-O, and 7.6% O-C=O. Similar to CPAC, the C (1s) peak region consisted of 42.6% C-C, 41.8% C-O, and 15.6% O-C=O. Furthermore, the sulfur contents of PCB and CBPAC were both 0.5%. The S (2p) peak region of PCB consisted of 58.9% ZnS (zinc sulfide) and 41.1% S=C=S. For CBPAC, the S (2p) peak region solely contained S=C=S. The comparison of two sulfur impregnation processes revealed that the innovative compositive impregnation process could simultaneously increased the sulfur content and the BET surface area of powdered activated carbon (PAC), however, the direct impregnation process increased the sulfur content while the BET surface area of PAC decreased linearly. Without the disadvantages of time and energy consumption associated with direct impregnation, the compositive impregnation is an efficient and energy-saving process for producing sulfurized PAC with a high BET surface area and high sulfur content. Experimental results obtained from the adsorption column tests indicated that the influence of the adsorption depth on the adsorptive capacity of CBPAC did not vary much, while the adsorptive capacity of CBPAC increased with HgCl2 concentration. Furthermore, the adsorptive capacity of CBPAC on vapor-phase HgCl2 was less than that of CPAC at the adsorption temperatures of 25~150¢J and high humidity of 12.3 wt %. The difference of adsorptive capacity for CBPAC and CPAC correlated closely with BET surface area and sulfur content. Results form the thermogravimetric adsorption analysis indicated that the adsorptive capacity of CBPAC and initial adsorption rate on vapor-phase HgCl2 increased with HgCl2 concentration and decreased with adsorption temperature. In the kinetic modeling, the deviation of experimental and simulated values simulated by the pseudo-first-order model was lower than those of pseudo-second-order models. Furthermore, the r (correlation coefficient) of pseudo-first-order and pseudo-second-order models were 0.9745~0.9977 and 0.9217~0.9780, respectively. It suggested that the pseudo-first-order model could simulate the adsorption of HgCl2 onto CBPAC better than pseudo-second-order model.

With increasing energy demand globally and, in particular, in South Africa coupled with depletion of the earth’s fossil energy resources and growing problem of disposal of nonbiodegradable waste such as waste tyres, there is a need and effort globally to find alternative energy from waste material including waste tyres. One possible way of exploiting waste tyre for energy or chemicals recovery is through gasification for the production of syngas, and this is what was investigated in this study. The possibility of gasification of waste tyre blended with coal after pyrolysis was investigated and two Bituminous coals were selected for blending with the waste tyre in co-gasification. A sample of ground waste tyre / waste tire, WT, a high vitrinite coal from the Waterberg coalfield (GG coal) and a high inertinite coal from the Highveld coalfield (SF coal) were used in this investigation. The waste tyre sample had the highest volatile matter content of 63.8%, followed by GG coal with 27% and SF coal with 23.8%. SF coal had the highest ash content of 21.6%, GG coal had 12.6% and waste tyre had the lowest of 6.6%. For the chars, SF char still had the highest ash of 24.8%, but WT char had higher ash, 14.7%, when compared to GG char with 13.9% ash. The vitrinite content in GG coal was 86.3%, whilst in SF coal it was 25% and SF coal had a higher inertinite content of 71% when compared to GG coal with 7.7%. SF char had the highest BET surface area of 126m2/g, followed by GG char with 113m2/g, and WT had the lowest value of 35.09m2/g. The alkali indices of the SF, WT and GG chars were calculated to be 8.2, 4.2 and 1.7 respectively. Coal samples were prepared by crushing and milling to particle sizes less than 75μm before charring in a packed bed balance reactor at temperatures up to 1000oC.Waste tyre samples were charred at the same conditions before milling to < 75μm particle size. Coal and WT chars were blended in ratios of 75:25, 50:50 and 25:75 before gasification experimentation. Carbon dioxide gasification was conducted on the blends and the pure coal and WT chars in a Thermogravimetric analyser (TGA) at 900oC, 925oC, 950oC and 975oC and ambient pressure. 100% CO2 was used at a flow rate of 2L/min. Reactivity of the pure char samples was found to be in the order SF > GG > WT, and the relationship between the coal chars’ reactivities could be explained by the high ash content of the SF char and low reactivity of the WT char corresponds to its low BET surface area. In general, the coal/WT char mixtures were less reactive than the respective coal, but more reactive than the pure WT char, the only exception being the 75% GG char blend which was initially more reactive than the GG char, and reactivity decreased with increasing WT content. For all samples reactivity increased with increasing temperature. The relationship between the reactivities of the GG char and its blends and that of the SF char and its blends was found to be affected by the amount of WT char added, especially at the lower temperatures 900oC and 925oC. SF coal is more reactive than GG coal, but at 900oC and 925oC, the reactivity of GG/WT blends improves in relation to the SF/WT blends with an increase in the ratio of WT in the blends, i.e. the 25% GG char blend is more reactive than the 25% SF char blend. The reactivity of the coal/WT blends was also checked against predicted conversion rates based on the conversion rates of the pure WT and coal samples. At 900oC and 925oC, the reactivities of the blends of both coal chars with WT char were found to be greater than the predicted conversion rates, and for the GG/WT blends the deviation increased with increasing WT ratios, while for the SF/WT blends the deviation increased with increasing SF ratios. These findings suggest the presence of synergism or enhancement between the coal chars and WT char in gasification reactions. The random pore model (RPM) was used to model the gasification results and it was found to adequately describe the experimental data. Activation energies determined with the RPM were found to be 205.4kJ/mol, 189.9kJ/mol and 173.9kJ/mol for SF char, WT char and GG char respectively. The activation energies of the coal/WT blends were found to be lower than those of both the pure coal and the pure WT chars. For the GG/WT blends the activation energy decreased with increasing WT char ratio, while for the SF/WT blends the activation energy decreased with increasing SF char ratio. The trends of the activation energies and conversion rates of the blends point to synergism or enhancement between the coal and WT chars in CO2 gasification reactions, and in the GG/WT blends this enhancement is driven more by the WT char, while in SF/WT blends it is driven by SF chars. It is possible that enhancement of the reactions is caused by mineral matter catalysis of the gasification reactions. The ash contents and alkali indices of the pure samples follow the order SF > WT > GG. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

With increasing energy demand globally and, in particular, in South Africa coupled with depletion of the earth’s fossil energy resources and growing problem of disposal of nonbiodegradable waste such as waste tyres, there is a need and effort globally to find alternative energy from waste material including waste tyres. One possible way of exploiting waste tyre for energy or chemicals recovery is through gasification for the production of syngas, and this is what was investigated in this study. The possibility of gasification of waste tyre blended with coal after pyrolysis was investigated and two Bituminous coals were selected for blending with the waste tyre in co-gasification. A sample of ground waste tyre / waste tire, WT, a high vitrinite coal from the Waterberg coalfield (GG coal) and a high inertinite coal from the Highveld coalfield (SF coal) were used in this investigation. The waste tyre sample had the highest volatile matter content of 63.8%, followed by GG coal with 27% and SF coal with 23.8%. SF coal had the highest ash content of 21.6%, GG coal had 12.6% and waste tyre had the lowest of 6.6%. For the chars, SF char still had the highest ash of 24.8%, but WT char had higher ash, 14.7%, when compared to GG char with 13.9% ash. The vitrinite content in GG coal was 86.3%, whilst in SF coal it was 25% and SF coal had a higher inertinite content of 71% when compared to GG coal with 7.7%. SF char had the highest BET surface area of 126m2/g, followed by GG char with 113m2/g, and WT had the lowest value of 35.09m2/g. The alkali indices of the SF, WT and GG chars were calculated to be 8.2, 4.2 and 1.7 respectively. Coal samples were prepared by crushing and milling to particle sizes less than 75μm before charring in a packed bed balance reactor at temperatures up to 1000oC.Waste tyre samples were charred at the same conditions before milling to < 75μm particle size. Coal and WT chars were blended in ratios of 75:25, 50:50 and 25:75 before gasification experimentation. Carbon dioxide gasification was conducted on the blends and the pure coal and WT chars in a Thermogravimetric analyser (TGA) at 900oC, 925oC, 950oC and 975oC and ambient pressure. 100% CO2 was used at a flow rate of 2L/min. Reactivity of the pure char samples was found to be in the order SF > GG > WT, and the relationship between the coal chars’ reactivities could be explained by the high ash content of the SF char and low reactivity of the WT char corresponds to its low BET surface area. In general, the coal/WT char mixtures were less reactive than the respective coal, but more reactive than the pure WT char, the only exception being the 75% GG char blend which was initially more reactive than the GG char, and reactivity decreased with increasing WT content. For all samples reactivity increased with increasing temperature. The relationship between the reactivities of the GG char and its blends and that of the SF char and its blends was found to be affected by the amount of WT char added, especially at the lower temperatures 900oC and 925oC. SF coal is more reactive than GG coal, but at 900oC and 925oC, the reactivity of GG/WT blends improves in relation to the SF/WT blends with an increase in the ratio of WT in the blends, i.e. the 25% GG char blend is more reactive than the 25% SF char blend. The reactivity of the coal/WT blends was also checked against predicted conversion rates based on the conversion rates of the pure WT and coal samples. At 900oC and 925oC, the reactivities of the blends of both coal chars with WT char were found to be greater than the predicted conversion rates, and for the GG/WT blends the deviation increased with increasing WT ratios, while for the SF/WT blends the deviation increased with increasing SF ratios. These findings suggest the presence of synergism or enhancement between the coal chars and WT char in gasification reactions. The random pore model (RPM) was used to model the gasification results and it was found to adequately describe the experimental data. Activation energies determined with the RPM were found to be 205.4kJ/mol, 189.9kJ/mol and 173.9kJ/mol for SF char, WT char and GG char respectively. The activation energies of the coal/WT blends were found to be lower than those of both the pure coal and the pure WT chars. For the GG/WT blends the activation energy decreased with increasing WT char ratio, while for the SF/WT blends the activation energy decreased with increasing SF char ratio. The trends of the activation energies and conversion rates of the blends point to synergism or enhancement between the coal and WT chars in CO2 gasification reactions, and in the GG/WT blends this enhancement is driven more by the WT char, while in SF/WT blends it is driven by SF chars. It is possible that enhancement of the reactions is caused by mineral matter catalysis of the gasification reactions. The ash contents and alkali indices of the pure samples follow the order SF > WT > GG. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Made available in DSpace on 2014-12-17T14:07:22Z (GMT). No. of bitstreams: 1 FranciscoASJ_TESE.pdf: 8792658 bytes, checksum: 82015e9b1bc788b7c608317086cdc276 (MD5) Previous issue date: 2014-05-30 / Researches have shown that the introduction of rubber in concrete improves the features of its deformability, as well as contributes to environmental disposal of waste generated in the tire retreading process. Furthermore, there is a high availability of limestone within RN and CE country. Ignorance about this stone, does not allow its wide use as aggregate, leaving, this abundant supply idle. A composite of limestone gravel, with proportions of tire rubber waste which could be used as concrete would be an alternative to concrete for low applications. Therefore, this research aims to evaluate the characteristics of concrete containing limestone gravel and proportions of little aggregate replacement (sand) by tire rubber waste. To this goal, the material components of the concrete were characterized, concrete specimens with limestone gravel were made, from the dash 1.0: 2.5: 3.5, varying the water/cement ratio, and inserting a commercial plasticizer, without a proportion of residue, known as reference. From this, concrete with and without the presence of the additive in the same proportions were chosen, as well as these with the use of granite gravel, for being the most used. Selected the references, to these, replacements of little aggregate (sand) were added replaced by rubber waste from the tire retreading process, treated with 1M NaOH in proportions from 5.0 to 20.0 % by mass, cured and exposed to the semiarid environment. The results indicate the possibility of using limestone gravel in the concrete composition with workability correction using plasticizer. There was a decrease in the mechanical properties of the concrete with increments of waste rubber, but there is an improvement in toughness and deformability of the composite, which makes it interesting for the construction of non-structural concrete floors, as well as, the rubber waste delayed the hardening process, continuing to gain resistance after 28 days / Pesquisas t?m mostrado que a introdu??o de borracha no concreto melhoram as caracter?sticas de deformabilidade deste, assim como, contribuem para destina??o ambiental de res?duos gerados no processo de recauchutagem de pneus. Somado a isto, existe uma alta disponibilidade de rocha calc?ria no interior do RN e do CE. O n?o conhecimento desta pedra, n?o possibilita sua ampla utiliza??o como agregado, deixando, esta farta oferta ociosa. Um comp?sito de brita do tipo calc?ria, com propor??es de res?duo de borracha de pneu que pudesse ser utilizado como concreto seria uma alternativa para concretos destinados a baixas solicita??es. Logo, este trabalho possui como objetivo a avalia??o das carater?sticas de concretos contendo brita calc?ria e propor??es de substitui??o do agregado mi?do (areia) por res?duo de borracha de pneus. Para tanto, caracterizou-se os materiais componentes do concreto, confeccionou-se corpos de prova de concretos com brita calc?ria, a partir do tra?o 1,0: 2,5: 3,5, variando-se a rela??o ?gua/cimento, e inserindo-se um plastificante comercial, sem a propor??o de res?duo, chamados de refer?ncia. A partir deste, foram escolhidos nas mesmas propor??es concretos com e sem a presen?a do aditivo, assim como, estes com a utiliza??o da brita gran?tica, por ser a mais utilizada. Escolhidas as refer?ncias, a estas foram acrescidas substitui??es de parte do agregado mi?do (areia) por res?duo de borracha de pneu proveniente do processo de recauchutagem, tratados com NaOH 1 M, nas propor??es de 5,0 a 20,0 % em massa, curados e expostos ao ambiente semi?rido. Os resultados indicam a possibilidade de utiliza??o da brita calc?ria na composi??o do concreto com corre??o da trabalhabilidade utilizando-se plastificante. Observou-se uma diminui??o nas propriedades mec?nicas dos concretos com incrementos de res?duo de borracha, por?m existe uma melhora de tenacidade, e deformabilidade do comp?sito, o que o torna interessante para a constru??o de pisos de concretos n?o estruturais, assim como, o res?duo retardou o processo de endurecimento, continuando o concreto a ganhar resist?ncia, ap?s os 28 dias

Submitted by Liliane Ferreira (ljuvencia30@gmail.com) on 2018-02-02T13:56:01Z No. of bitstreams: 2 Dissertação - Ruvier Rodrigues Pereira - 2018.pdf: 24207459 bytes, checksum: 94fa95ed93dc7a1c42a8b41aea55d2e9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-02-02T14:32:35Z (GMT) No. of bitstreams: 2 Dissertação - Ruvier Rodrigues Pereira - 2018.pdf: 24207459 bytes, checksum: 94fa95ed93dc7a1c42a8b41aea55d2e9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-02-02T14:32:35Z (GMT). No. of bitstreams: 2 Dissertação - Ruvier Rodrigues Pereira - 2018.pdf: 24207459 bytes, checksum: 94fa95ed93dc7a1c42a8b41aea55d2e9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-01-30 / Fundação de Amparo à Pesquisa do Estado de Goiás - FAPEG / The volume of solid waste produced is increasing disorderly and harmful to nature, since they are not given him proper purposes. As waste that can be used in the manufacture of concrete bricks is the waste tire rubber, which is a major cause of environmental problems, and the cementitious waste generated in concrete plants, called Concrete Sludge Waste (CSW). The overall objective of this study will then be to determine a concrete trait for brick production, containing the highest percentages of concrete sludge waste and tire rubber granulate together. To do so, the applicability of the residues was analyzed separately in Studies 1 and 2, and later jointly in Study 3, that the Central Composite Delineation of Rotational was used as experimental planning and the data evaluated through Response Surface Methodology, and Study 4, being the waste tire rubber granulate replacing the aggregate and the Concrete Sludge Waste in its dry state (CSW-S) to the cement. The physical-chemical characterization of the aggregates and the test of resistance to compression and water absorption of the bricks were performed. The results showed that it is feasible to use CSW-S and waste tire rubber granulate, but the higher the rubber percentage, the lower the compressive strength and the higher the water absorption, the rubber substitution limit is dependent on the aggregate used and the molding conditions, as well as the trace used. However, the CSW-S did not present significant effects when compared to those of the rubber, thus, replacements of higher percentages could be made. There is then an optimal trace with about 4% rubber aggregate substitution and approximately 15% LRC-S, replacing the cement. However, it can be affirmed that the use of concrete bricks with residue for sealing is technically feasible, in order to reduce the volume of discarded waste, obtain a cheaper product and still meet the criteria required by the standards. / O volume de resíduos sólidos produzido vem aumentando de modo desordenado e prejudicial à natureza, uma vez que não são dados a ele fins adequados. Como resíduos passíveis de se utilizar na fabricação de tijolos de concreto se tem a borracha de pneus, que é um grande causador de problemas ambientais, e o resíduo cimentício gerado em usinas de concreto, denominado de Lama Residual do Concreto (LRC). O objetivo geral deste estudo será, então, determinar um traço de concreto para produção de tijolos, que contenha maiores porcentagens de resíduos de usinas de concreto e de borracha de pneu, conjuntamente. Para tanto, foram analisadas a aplicabilidade dos resíduos separadamente, nos Estudos 1 e 2, e posteriormente de forma conjunta no Estudo 3, que foi utilizado o Delineamento Composto Central Rotacional como planejamento experimental e os dados avaliados via Metodologia de Superfície de Resposta, e Estudo 4, sendo o granulado de borracha em substituição ao agregado e a Lama Residual do Concreto em seu estado seco (LRC-S) ao cimento. Foram realizadas a caracterização físico-química dos agregados e ensaio de resistência à compressão e absorção de água dos tijolos. Os resultados mostraram que é viável se utilizar a LRC-S e o granulado de borracha de pneu, porém quanto maior a porcentagem de borracha, menor será a resistência à compressão e maior será a absorção de água, sendo que o limite de substituição da borracha é dependente do agregado empregado e das condições de moldagem, bem como do traço utilizado. Já a LRC-S não apresentou efeitos significativos se comparados com aqueles da borracha, podendo ser feitas, assim, substituições de maiores porcentagens. Tem-se, então, um traço ótimo com cerca de 4% de substituição do agregado por borracha e com aproximadamente 15% de LRC-S, em substituição ao cimento. Contudo, pode se afirmar que a utilização de tijolos de concreto com resíduo para vedação é viável tecnicamente, de forma a diminuir o volume de resíduos descartados, obter um produto mais barato e ainda atender aos critérios exigidos pelas normas.

M.Tech. (Department of Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / The generation of waste tires is one of the most serious environmental problems in the modern world due to the increased use of auto mobiles all over the world. Currently there is a problem with the disposal of waste tires generated since there are strict regulations concerning their disposal through landfill sites. Therefore, there is a need to find ways of disposing these waste tires which pose serious health and environmental problem. The pyrolysis of the waste tires has been recognised as the most promising method to dispose the waste tires because it can reduce the weight of the waste tires to 10% of its original weight and produce products such as pyrolysis oil, pyrolysis char, and pyrolysis char. These products can be further processed to produce value added products. The char produced from the pyrolysis of waste tires can be further activated to produce activated carbon. This study is based on the chemical activation of waste tire pyrolysis char to produce activated carbon for the removal of lead ions from aqueous solution. This was done by impregnating the waste tire pyrolysis char with Potassium hydroxide and activating it inside a tube furnace under inert conditions to produce waste tire activated carbon. Adsorbent characterisation techniques (SEM, FTIR, TGA, XRF, XRD, BET, and Proximate analysis) were performed on the waste tire pyrolysis char and the activated carbon produced to make a comparison between the two samples. The results showed that the waste tire activated carbon produced has better physical and chemical properties compared to the raw waste tire pyrolysis char. Adsorption results revealed that waste tire activated carbon achieves higher removal percentages of lead ions from aqueous solution compared to waste tire pyrolysis char. The results also showed the effect of various process variables on the adsorption process. Adsorption isotherms, kinetics, and thermodynamics were also studied. The adsorption of lead ions agreed with the Freundlich isotherm model for both the waste tire pyrolysis char and waste tire activated carbon. In terms of adsorption kinetics, the experimental data provided best fits for the pseudo-first order kinetic model for both the waste tire pyrolysis char and the waste tire activated carbon. The adsorption thermodynamics study revealed that the process is an exothermic process and spontaneous in nature. Response surface methodology was used to determine the combined effect of process variables on the adsorption of lead ions onto waste tire activated carbon and to optimise the process using numerical optimisation. The optimum conditions were found to be adsorbent dosage = 1g/100ml, pH = 7, contact time = 115.2 min, initial meta concentration = 100 mg/l, and temperature = 25°C to achieve a maximum adsorption capacity of 93.176 mg/l.

Made available in DSpace on 2016-06-02T19:53:34Z (GMT). No. of bitstreams: 1 STARK_Felipe_2015.pdf: 2619946 bytes, checksum: 296213b74067cc59aea0beae2cf8f165 (MD5) Previous issue date: 2015-03-20 / Universidade Federal de Minas Gerais / The increase in the municipal and industrial waste generation has caused enviromental and public health problems and as a consequence laws exist to address the issue. In Brazil, with the Federal Law No. 12,350 / 10 about the Política Nacional de Resíduos Sólidos reverse logistics (RL) of some products has become mandatory, including waste tires. However, RL of waste tires has been structured since environmental government agency resolutions propose treatment for tires disposal incorrectly in the environment and new generation of waste tires. Currently, the reverse network is managed by the tire manufacturers and importers associations, and destinations are commonly used are co-processing in cement kilns, and the recovery of rubber and steel as secondary products, by processes such as scrapping or lamination. Increasing transportation and operation costs in the logistics network make the network design critical for the full compliance with the legal goal. This network design is aligned with a planning that considers the financial issues like the minimization of costs or the maximization of profit, while meets the requirements of environmental government agencies. So it involves key strategic decisions, as the location of facilities and material flows, taking into account many parameters simultaneously. The objective of this study is to propose a model for waste tires reverse logistics considering: (i) flows from the output of the collection points (called ecopontos ) to the destination companies; (ii) the possibility of processes as the sorting of used tires in usable condition or not; (iii) the grinding process as an intermediate phase and for which type of destination the tire would be sent. Still are considered fixed costs for the installation of storage centers, for sorting used tires, and intermediary companies, for grinding and separation of components, in addition to the variable operating costs, transportation and potential revenues generated from the substitution of raw materials or fuel in destination companies. The model is a mixed integer linear problem (MILP) with multiple time periods. Experiments are done with a single and multiple periods, finally were present some sensitivity analysis. Other financial constraints as the annual budget and an approach that includes the carbon footprint (CO2) in the transport and processing are explored. The results showed configurations that meet the goal and have a small profit, indicating that storage centers are preferred in places far from destination points and low demand, while the pre-processing companies have opposite behavior. When using the carbon footprint, it was found that the sorting of used tires gain more importance in the view of reducing emissions, because there is less emission in the reuse or refurbishment compared to the manufacturing of new tires. / O aumento na geração de resíduos urbanos e industriais tem ocasionado problemas de ordem ambiental e de saúde pública, e, como consequência, legislações específicas surgiram para tratar do assunto. No Brasil, a Lei Federal nº 12.350/10, da Política Nacional de Resíduos Sólidos, tornou obrigatória a logística reversa (LR) de alguns produtos, entre os quais o pneu usado sem condição de rodagem (inservível). Entratanto, a LR de pneus inservíveis já se apresentava em fase de estruturação, uma vez que resoluções ambientais propunham o tratamento do passivo deixado por anos de descarte incorreto dos pneus no meio ambiente. Atualmente, a rede reversa de pneus é administrada por associações de fabricantes e importadores, e as destinações comumente utilizadas são o coprocessamento, em fornos de cimenteira, e a recuperação da borracha e do aço como subprodutos, por meio de processos como a granulação ou a laminação. Os crescentes custos do transporte terrestre e as proposições de melhorias na rede logística tornam a configuração da rede de logística reversa de pneus como uma proposta para o total cumprimento da meta, alinhados ao planejamento que considere as questões financeiras como a minimização de custos logísticos ou maximização do lucro, enquanto cumprem as exigências dos órgãos ambientais. Esta configuração envolve decisões estratégicas essenciais, como a localização de instalações e determinação dos fluxos de materiais, sendo que muitos parâmetros estão presentes simultaneamente. O objetivo deste estudo é propor um modelo de configuração de rede logística reversa de pneus inservíveis considerando: (i) fluxos a partir da saída dos pontos de coleta (ecopontos) até as empresas destinadoras; (ii) processos como a possibilidade da triagem dos pneus usados em servíveis e inservíveis; (iii) a trituração como fase intermediária e para qual tipo de destinação enviar. São considerados ainda custos fixos para instalação de centros de armazenamento, para triagem dos pneus usados, e empresas intermediárias, para trituração e separação de componentes, além dos custos variáveis de operação, transporte e as possíveis rendas geradas com a substituição da matéria-prima ou combustível nas empresas destinadoras. O modelo apresenta formulação linear inteira mista (MILP) com múltiplos períodos. São feitos experimentos com único período, e com a variação de parâmetros. Posteriormente são estudadas restrições financeiras como orçamento anual e uma abordagem que inclui a pegada de carbono (CO2) no transporte e processamento. Os resultados encontrados apresentaram configurações que cumprem a meta e apresentam um pequeno lucro, indicando que os centros de armazenamento são preferíveis em locais afastados das destinadoras e com baixa demanda, enquanto as empresas intermediárias apresentam comportamento oposto. Quando se utilizou a pegada de carbono, verificou-se que a triagem de pneus ganha mais importância, dada a redução nas emissões do reuso ou reforma dos pneus em relação à fabricação de novos pneus.

L’objectif de ces travaux de recherche était de synthétiser de mousses polyuréthane (PUF) bio-basées à partir d’oligomères hydroxytéléchéliques issus du caoutchouc naturel (HTNR) ou à partir de poudrettes de pneus usagés (HTWT) et du diol de la polycaprolactone (PCL) comme segments soft. Les paramètres étudiés ont été le type de polyol et le rapport molaire entre HTNR/PCL et HTWT/PCL. La masse molaire de HTNR, HTWT et PCL étaient respectivement 1,800, 1400 et 2000 g/mol. L’effet du rapport molaire HTNR/PCL et HTWT/PCL (1/0, 1/0/5/, 1/1, et 0.5/1) sur la vitesse de formation des mousses et sur les propriétés chimiques et physiques a été étudié. Les structures chimiques de HTNR, HTWT et PUF ont été confirmées par FTIR et 1H-RMN. Le diol de la PCL était le plus réactif donc augmentant le contenu de PCL-diol la vitesse de formation des mousses a augmenté. La densité des mousses a changé légèrement avec le rapport molaire cependant la résistance à la traction reste dans la même gamme. Le diamètre moyen des cellules a augmenté en fonction du contenu de PCL-diol et la tendance inverse a été observée pour l’allongement à la rupture et la résistance à la compression. L’observation au microscope électronique à balayage (MEB) a montré que les mousses basées sur les HTNR étaient alvéolées et fermées. La biodégradabilité a été évaluée selon le test de Sturm. Polyéthylène à baisse densité et benzoate de sodium ont été utilisés respectivement comme témoins négatif et positif. Les mousses ont montré une période d’induction de 33 jours dans lequel le pourcentage de dégradation était ~ 7-10%. La biodégradation de PUF contenant seulement HTNR a été 8.4% après 28 jours et 31.89% après 60 jours ; les PUF contenants 1/0.5 HTNR/PCL ont montré un pourcentage supérieure : 11.31% après 28 jours et 45.6% après 60 jours. Le rapport molaire HTWT/PCL a influencé beaucoup la vitesse de formation des mousses et leur morphologie. Cellules fermées de forme polyédrique ont été observé par microscopie électronique à balayage. Les résultats de l’analyse thermogravimétrique ont montré que l’addition du diol de la PCL a augmenté la température de dégradation. Il a été observé qu’une basse vitesse de réaction génère des mousses à haute densité, petit diamètre de cellule et haute distribution des diamètres. La biodégradation des PUF contenant seulement HTWT a été 31.2% après 28 jours et 51.3% après 60 jours, tandis que les PUF contenant 1/0.5 HTWT/PCL ont montré une dégradation plus élevée : 39.1% après 28 jours et 64.3% après 60 jours. La vitesse de formation des mousses basées sur les HTWT était supérieure à celle des mousses basées sur les HTNR. Toutes les mousses basées sur les HTWT ont une densité supérieure et une taille de cellule inférieure à celles basées sur HTNR. La structure des cellules des mousses basées sur les HTNR ou HTWT était différente cependant toutes les mousses ont montré des cellules quasi complètement fermées. Les mousses basées sur les HTWT ont montré des propriétés thermiques et de biodégradation meilleures par rapport aux mousses basées sur les HTNR. / The aim of this research was to prepare a bio-based polyurethane foam (PUF) containing hydroxyl telechelic oligomers from natural rubber (HTNR) and waste tire crumbs (HTWT) and polycaprolactone diol (PCL) as soft segments. The studied parameters included type of polyols and molar ratio between HTNR/PCL and HTWT/PCL. The molecular weight of HTNR and HTWT derived from 1H-NMR spectra were 1,800 and 1,400 g/mol, respectively. The molecular weight of PCL diol was 2000 g/mol. The effect of HTNR/PCL and HTWT/PCL molar ratio (1/0, 1/0.5, 1/1 and 0.5/1) on the foam formation rate and physical and chemical properties of the resulting PUF was investigated. The chemical structure of HTNR, HTWT and PUF were confirmed by FTIR and 1H-NMR. PCL diol provided faster reaction, thus higher PCL diol content showed higher foam formation rate. The foam density slightly changed with the molar ratio whereas the specific tensile strength of all samples was in the same range. The average diameter of cell increased with increasing contents of PCL diol. The addition of PCL diol resulted in reduced elongation at break and compressive strength. The cellular structure observed by SEM micrographs of HTNR based foams showed an almost closed cell. The biodegradability was assessed according to a modified Sturm test. Low density polyethylene and sodium benzoate were used as a negative and positive control sample, respectively. PUF samples showed an induction time of 33 days in which the percentage of biodegradation was  7-11%. The biodegradation of PUF containing only HTNR was 8.4% and 31.89% at 28 days and 60 days of testing respectively whereas the PUF containing 1/0.5 HTNR/PCL (by mole) showed a higher biodegradation: 11.31% and 45.6% at 28 days and 60 days of testing respectively. The molar ratio of HTWT/PCL strongly affected the kinetic rate of foam formation and foam morphology. According to SEM micrographs, polyhedral closed cells were observed. The addition of the PCL diol increased the thermal degradation temperature of the PUF based on TGA results. A low kinetic rate provided PUF with a high density, small cell size and a broad cell size distribution. The biodegradation of PUF containing only HTWT was 31.2% and 51.3% at 28 days and 60 days of testing respectively whereas the PUF containing 1/0.5 HTWT/PCL diols (by mole) showed a higher biodegradation: 39.1% and 64.3% at 28 days and 60 days of testing respectively. The foam formation rate of HTWT based PUF was higher than the one of HTNR based PUF. All HTWT based PUF have a higher density than HTNR based PUF. The HTWT based PUF had an inferior cell size in comparison to HTNR based PUF. The cellular structure of HTNR based and HTWT based PUF were different, but all PUFs showed almost closed cells. The HTWT based PUF had a higher thermal degradation temperature and biodegradation properties than foams from HTNR. / วัตถุประสงค์ของงานวิจัยนี้ เพื่อทำการเตรียมโฟมพอลิยูรีเทนชีวภาพ (PUF) จากยางธรรมชาติดัดแปรที่มีหมู่ปลายไฮดรอกซิล (HTNR) ยางคลัมบ์ดัดแปรที่มีหมู่ปลาย ไฮดรอกซิล (HTWT) และพอลิคาโปรแลคโทน (PCL) ศึกษาผลของชนิดพอลิออล และสัดส่วนโดยโมลระหว่าง HTNR/PCL และ HTWT/PCL ที่สัดส่วน 1/0, 1/0.5, 1/1 และ 0.5/1 โดยโมล นํ้าหนักโมเลกุลของ HTNR, HTWT และ PCL ที่ใช้สำหรับงานวิจัยนี้ คำนวณจาก 1H-NMR คือ 1,800, 1,400 และ 2,000 g/mol ตามลำดับ ลักษณะโครงสร้างทางเคมีของ HTNR, HTWT และPUF สามารถวิเคราะห์และยืนยันด้วยเทคนิค FTIR และ 1H-NMR รวมถึงทำการวัดอัตราการก่อโฟม (Foam formation rate) ทดสอบสมบัติทางกายภาพ ทางเคมี และสมบัติการย่อยสลายทางชีวภาพ พบว่าในกรณีของโฟมพอลิยูรีเทนจาก HTNR/PCL เมื่อใช้ PCL ในปริมาณที่มากขึ้นจะส่งผลให้อัตราการก่อโฟมเร็วขึ้น และขนาดของเซลโฟมมีขนาดใหญ่ขึ้นด้วย ในขณะที่ค่าความหนาแน่น และความต้านทานต่อแรงดึงจำเพาะมีการเปลี่ยนแปลงเล็กน้อย การเติม PCL ในส่วนผสมของโฟมยังส่งผลให้ความสามารถในการยืด ณ จุดขาด และความทนทานต่อการกดมีค่าลดลง การคืนตัวหลังการกดของโฟม PUF2 (สัดส่วนระหว่าง HTNR/PCL = 1/0.5) จะให้ค่าตํ่าที่สุดคือ 40% ลักษณะของโฟมที่ได้จากการทดลองนี้โดยส่วนใหญ่จะเป็นแบบเซลปิด ความสามารถในการย่อยสลายทางชีวภาพของโฟม ทดสอบโดยใช้วิธี Sturm Test มี LDPE เป็นตัวเปรียบเทียบเชิงลบ และใช้ Sodium benzoate เป็นตัวเปรียบเทียบเชิงบวก พบว่าโฟมเริ่มมีการย่อยสายเกิดขึ้นอย่างเห็นได้ชัดที่เวลา 33 วัน มีเปอร์เซ็นต์การย่อยสลายในช่วง 7-11 เปอร์เซ็นต์ เปอร์เซ็นต์การย่อยสลายของโฟมจาก HTNR (PUF1) อยู่ที่ระดับ 8.4 และ 31.89 เปอร์เซ็นต์ และเปอร์เซ็นต์การย่อยสลายของโฟมจาก HTNR/PCL (1/0.5) อยู่ที่ระดับ 11.31 และ 45.6 เปอร์เซ็นต์ ที่เวลาในการทดสอบ 28 และ 60 วัน ตามลำดับ กรณีของโฟมพอลิยูรีเทนจาก HTWT/PCL เมื่อใช้ PCL ในปริมาณที่มากขึ้นจะส่งผลให้ค่าความหนาแน่นสูงขึ้น ขนาดของเซลโฟมลดลงมีการกระจายของเซลในวงกว้างไม่สมํ่าเสมอ เปอร์เซ็นต์การย่อยสลายทางชีวภาพของโฟมจาก HTWT (PUF5) อยู่ที่ระดับ 31.2 และ 51.3 เปอร์เซ็นต์ และเปอร์เซ็นต์การย่อยสลายของโฟมจาก HTWT/PCL (1/0.5) อยู่ที่ระดับ 39.1 และ 64.3 เปอร์เซ็นต์ ที่เวลาในการทดสอบ 28 และ 60 วัน ตามลำดับ เมื่อทำการเปรียบเทียบโฟมที่ได้จากการเตรียมโดยใช้พอลิออลหลักเป็น HTNR และ HTWT พบว่าโฟมจากพอลิออลหลัก HTWT ให้อัตราการก่อตัวของโฟมเร็วกว่า ขนาดของเซลโฟมเล็กกว่า ความหนาแน่น ความต้านทานต่อความร้อน และเปอร์เซ็นต์การย่อยสลายทางชีวภาพสูงกว่า เมื่อเทียบกับโฟมจากพอลิออลหลัก HTNR

Scrap tyres provide numerous advantages from the viewpoint of civil engineering practices. Scrap tyres are light weight, have high vibration absorption, high elastic compressibility, high hydraulic conductivity, and temperature isolation potential. Scrap tyres have a thermal resistivity that is about seven times higher than soil; they produce low earth pressure and absorb vibrations. Many new techniques have emerged with time to utilize these advantageous characteristics for practical purposes in civil engineering. Though current reuse and recovery of scrap tyres has reduced the amount of landfills, but still there is a need for developing additional practices for the reuse of scrap tyres. Moreover, most of present practices do not use its vibration absorption capacity efficiently. To use the scrap tyres as individual material or mixed with soil in civil engineering applications, the systematic understanding of static and dynamic properties of sand-rubber mixtures (SRM) are of prime importance. In the present study an attempt has been made to characterize the SRM to use them as low-cost isolation material for low-to-medium rise buildings. Proposal of this isolation system using SRM is addressed in this study in four parts; in the first part, the estimation of shear strength and volumetric characteristics of the SRM were carried out. A total of seven different rubber sizes (six sizes of granulated rubber; 2 - 1 mm; 4.75 - 2 mm; 5.6 - 4.75 mm; 8 - 5.6 mm; 8 - 9.5 mm; 12.5 - 9.5 mm and one size of tyre chips; 20 - 12.5 mm) were considered for characterizing the SRM, and the rubber size which has higher shear strength characteristics is identified as optimum size for further studies. Second part deals with the effect of reinforcement on SRM with higher rubber content (50% and 75% rubber by volume). In the third part, dynamic properties of selected SRM combination with and without reinforcement were generated from experimental studies. In the last part, the numerical analysis was carried out using finite element program Strand7 to find out optimum dimension of proposed isolation scheme and reduction of spectral accelerations. In addition, the laboratory model tests were also carried out on square footing supported on unreinforced and reinforced SRM. The relative performances of reinforcement on settlement characteristics of SRM for 50% and 75% SRM have been compared with unreinforced SRM. Engineering behaviour of SRM has been studied by considering different rubber sizes and compositions by carrying out large scale direct shear test and Unconsolidated Undrained (UU) triaxial test. The shear strength characteristics such as peak shear stress, cohesion, friction angle, secant/elastic modulus, volumetric strain, failure and ultimate strength, ductility/brittleness index, and energy absorption capacity of sand and SRM were determined. The optimum percentage rubber content based on maximum shear strength and energy absorption capacity has been arrived. The granulated rubber size (12.5 - 9.5 mm) and percentage ratio, 30% by volume is found to be optimum size and content, which gives the maximum energy absorption capacity and lower brittleness index values compared to other rubber sizes. This chapter also describes the applicability of concept of Response Surface Methodology (RSM) to identify an approximate response surface model from experimental investigations on the engineering properties of sand and SRM. The experimental data were quantitatively analyzed by multiple regression models by correlating response variables with input variables in this study. To consume more tyres in SRM, rubber mix of 50 % and 75 % mixes are studied and these SRM results in lower shear strength and higher volume change when compared to 30 % SRM. To improve shear strength and reduce compressibility, geosynthetic reinforcement study has been carried out for 50% and 75% rubber by volume. Here geotextile, geogrid and geonets were used as reinforcement and number of layers and spacing between layers were varied. Finally type of reinforcement, number of layers and optimum spacing are arrived for the optimum rubber size of 12.5 - 9.5 mm for reinforced SRM. This study found that 4 layers with equal spacing of geotextile for 50 % SRM and geonet for 75 % SRM shows better strength when compared to other combinations. Further dynamic properties such as shear modulus and damping values at different strain level are estimated for red soil, sand, 30 % SRM and unreinforced and reinforced 50 % and 75 % SRM by carrying out resonant column tests and cyclic triaxial tests. The normalized shear modulus and damping ratio curves have been developed for these materials. The experimental results indicate that, shear modulus increases for 30% rubber by volume when compared to sand, thereafter the shear modulus values decreased with a further increase in rubber content in SRM. Whereas the damping ratio increases with increasing rubber content in SRM. For sand and SRM, with an increase in confining pressure shear modulus increases and damping ratio decreases. Based on the comprehensive set of experimental results, a modified hyperbolic model has been proposed. These properties are further used in the numerical analysis to find out the effectiveness of SRM as isolation material. Numerical dynamic analysis has been carried out on a 2-D finite element model of the soil-foundation-structure system. The building model has been generated considering the typical G+2 building resting on 20 m thick soil followed by rock depth and foundation is placed at 2.0 m below ground level. The beams and columns in the superstructure are modeled using 2-D frame elements. The soil column has been modeled using 4-noded 2-D plane strain plate elements. Considering the transmitting boundary condition, viscous dampers are implemented at the base of the computational soil domain in order to mitigate the reflective effects of waves. The Newmark family method (average acceleration method) has been used to calculate the displacement, velocity and acceleration vectors. Comprehensive numerical simulations have been carried out on the soil-foundation-structure system by varying rubber content in SRM (30%, 50% and 75% granulated rubber by volume), depth and thickness of SRM around footing and considering two input earthquake acceleration time history. It was found that earthquake vibrations are considerably reduced for SRM with higher rubber content. The optimum dimension of SRM giving maximum reduction in shaking level is found to be 3B below the footing and 0.75B (where B is the width of footing) on the side of the footing. Generally, the shaking levels at different floor can be reduced by 30-50%, with the use of 75% SRM. The results also indicated that the effectiveness of proposed system would depend on the characteristics of ground motion. To study the bearing capacity of square footing on SRM, laboratory model tests were carried out on square footing supported on unreinforced and reinforced SRM. The SRM combination which have been used for numerical studies are used in this model studies to know the bearing capacity and settlement characteristics. The optimum dimension of SRM around footing has been constructed. Model tests results show that, the bearing capacity decreases and settlement increases steadily with the increase in rubber content in SRM. Addition of reinforcement to SRM significantly improved the bearing capacity and reduced settlement characteristics. Reinforced SRM may be used as an effective low cost isolation scheme to reduce earthquake vibrations.